• Bulletin of the Korean Chemical Society
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• v.29 no.1
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• pp.177-180
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• 2008

Laser induced fluorescence studies of hydrogen atom using four wave mixing technique are reported for the photodissociation of CH4 and its isotopomers at Lya (121.6 nm). The source of dissociating and probe radiation is one and the same (delay time??20 nsec). The average translational energy of ejected hydrogen atoms (50 Kcal/mol) reveals that CH4 + hn??CH3 + H(2S) and CH4 + hn??CH2(a1A1) + H2(1Sg) are the main dissociation processes. The absolute quantum yield for CH4 and CD4 are the same, FH(CH4) = FD(CD4) = 0.31 0.05. If one divides the experimental H/D ratios from the isotopomers CH3D, CH2D2, CHD3 by the isotopic H/D ratios, a value 2 is obtained in all three cases. Overall, the heavier D atoms are more likely than the H atoms to remain attached to the carbon atom.

• Rapid Communication in Photoscience
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• v.4 no.4
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• pp.79-81
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• 2015

The influence of the grain size of the $CH_3NH_3PbI_3$ on the solar cell performance is investigated by controlling the ratio between $CH_3NH_3I$ and $PbI_2$ precursors. As the concentration of the precursors increased from 1.0M to 2.0M, the $CH_3NH_3PbI_3$ grain size increased from ~100nm to ~400nm. The solar cell utilizing the $CH_3NH_3PbI_3$ with large grain size shows improved photocurrent compared to the solar cell utilizing $CH_3NH_3PbI_3$ with small grain size, which is ascribed to the reduced recombination at the boundaries of grains.

• Macromolecular Research
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• v.16 no.5
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• pp.441-445
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• 2008

A series of aluminum complexes supported by $\beta$-ketoamino, ligand-bearing, 3-position substituents $LAlEt_2$ ($L=CH_3C(O)C(Cl)=C(CH_3)NAr\;(L_1)$, $L=CH_3C(O)C(H)=C(CH_3)NAr\;(L_2)$, $L=CH_3C(O)C(Ph)=C(CH_3)NAr\;(L_3)$, and $L=CH_3C(O)C(Me)=C(CH_3)NAr\;(L_4)$, $Ar=2,6-^iPr_2C6H_3$) were synthesized in situ and employed in the ring-opening polymerization (ROP) of $\varepsilon$-caprolactone ($\varepsilon$-CL) and cyclohexene oxide (CHO). The 3-position substituents on the $\beta$-ketoamino ligand backbone of the aluminum complexes influenced the catalyst activity remarkably for both ROP of $\varepsilon$-CL and CHO. Aluminum $\beta$-ketoamino complexes displayed different catalytic behavior in ROP of $\varepsilon$-CL and CHO. The order of the catalytic activity of $LAlEt_2$ was $L_1AlEt_2$>$L_2AlEt_2$>$L_3AlEt_2$>$L_4AlEt_2$ for ROP of $\varepsilon$-CL, being opposite to the electron-donating ability of the 3-position substituents on the $\beta$-ketoamino ligand, while the order of the catalytic activity for ROP of CHO was $L_1AlEt_2$>$L_3AlEt_2$>$L_4AlEt_2$>$L_2AlEt_2$. The effects of reaction temperature and time on the ROP were also investigated for both $\varepsilon$-CL and CHO.

• Journal of the Korean Chemical Society
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• v.43 no.4
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• pp.456-460
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• 1999

Rates of 1-adamantyl fluoroformate with substituted pyridines ($3-CH_3,\;4-CH_3,\;H,\;3-Cl,\;3,4-(CH_3)_2,\;3,5-(CH_3)_2$) in methanol have been measured by conductometric method at various temperatures and concentrations. The activation parameters (${\Delta}H^{\neq},\;{\Delta}S^{\neq}$) and Hammett reaction constant (${\rho}$) or Bronsted coefficient (${\beta}$) were evaluated from rate constants. The activation entropies are large and negative, and the activation enthalpies are small and positive. The Hammett reaction constant (${\rho}$) and Bronsted coefficient (${\beta}$) values were -4.15 and 0.63, respectively. From the above results, it may be concluded that this reaction proceeds to a concerted displacement mechanism in methanol.

• Bulletin of the Korean Chemical Society
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• v.18 no.3
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• pp.305-310
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• 1997

The synthesis and characterization of the platinum heterocyclic carboxaldehyde thiosemicarbazone complexes [NC5H4CRNNC(S)NHR'PtCl] (R=H, R'=CH3(1); R=CH3, R'=CH3(2); R=CH3, R=H(3)) and diphenylphosphinophenyl carboxaldehyde thiosemicarbazone complexes [Ph2PC6H4CHNNC(S)NHRPtCl] (R=CH3(5); R=iC3H7(6); R=Ph(7)) are described. Compounds 1-3 were prepared by reaction of Pt(SEt2)2Cl2 with 2-acetylpyridine-4-alkylthiosemicarbazone in the presence of NEt3. Compounds 5-7 were prepared using Pt(SEt2)2Cl2 in toluene with diphenylphosphinophenyl carboxaldehyde alkylthiosemicarbazone. The compounds have been characterized by microanalysis, NMR (1H, 13C, 31P) spectroscopy, and single-crystal X-ray diffraction. X-ray single crystal diffraction analysis reveals that compound 5 is a mononuclear platinum compound with P,N,S-coordination mode.

• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.1-7
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• 1980

Solvolysis rate constants for methylchloroformate, methylthionochloroformate, methylthiolchloroformate and methyldithiochloroformate have been determined conductometrically in methanol, ethanol and ethanol-water mixtures and activation parameters have been derived. Results show that methylchloroformate solvolyzes through $S_N2$ process while methyldithiochloroformate solvolyzes by $S_N1$ process in all the solvent systems. The rate of hydrolysis decreased in the order, $CH_3S(CS)Cl>CH_3S(CO)Cl>CH_3O(CS)Cl>CH_3O(CO)Cl$ which corresponds to the order of decreasing $S_N1$ character. In methanol, $CH_3S(CS)Cl$ solvolyzed via the $S_N1$ mechanism while the others solvolyzed via the $S_N2$ process. In ethanol, however, $S_N2$ character was dominant for all the compounds, except methyldithiochloroformate, for which $S_N1$ character was still strong enough to accelerate the rate of ethanolysis. In ethanol-water mixtures, $CH_3S(CS)Cl$ and $CH_3S(CS)Cl$ solvolyzed via $S_N2$ process in ethanol-rich region while the $S_N1$ character increased greatly in water-rich region for the solvolysis of these compounds. The order of $S_N1$ character for solvolysis in water-rich region was the same as the order of hydrolysis rate.

• Journal of the Korean Chemical Society
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• v.37 no.12
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• pp.1047-1052
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• 1993

The electronic spectra of enzyme-model organocobalt(Ⅲ) complexes containing completely or partially conjugated macrocyclic ligands were measured in various solvents to investigate the solvent effect on the charge transfer band for the axial cobalt-carbon bond by the extent of conjugation in the equatorial macrocyclic ring; completely conjugated, $CH_3CoL,\;C_6H_5CoL,\;CNCoL,\;CH_3CoL',\;CNCoL'$, partially conjugated $CH_3(py)Co(DH)_2, CH_3CoL＂$, unconjugated dienes, $[CH_3Co(1,4-CT)](ClO_4)_2$, and open ring, $CH_3Co(salen)$. The position of the charge transfer band which corresponds to the cobalt-carbon bond was shifted to a shorter wavelength as the polarity of solvent increased and the transition energy $(E_T)$ had a linear relationship with solvent polarity parameter, Z-value, only in the case of completely conjugated system. However, the linear correlation between $E_T$and Z was not observed for partially conjugated and open ring systems.

• Bulletin of the Korean Chemical Society
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• v.21 no.11
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• pp.1133-1137
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• 2000

Gibbs ensemble Monte Carlo simulations were performed to calculate the vapor- liquid coexistence properties for the binary mixtures $CO_2/C_3H8$, $CO_2/CH_3OCH_3$, and $CO_2/CH_3COCH_3.$ For all the molecules the potential between sites in different molecules was simply calculated by the Lennard-Jones potential. Density of the mixture, composition of the mixture, the pressure-composition diagram, the chemical potential of component, and the radial distribution function were calculated at vapor- liquid equilibrium. The composition and the density of both vapor and liquid from simulation agreed considerably well with the experimental values over a wide range of pressures. The radial distribution functions in the liquid mixtures showed that $CO_2$ molecules tended to form cluster with each other and $C_3H8$ molecules also aggregated each other due to the weak interaction between $CO_3$ and $C_3H8$ molecule. However the interaction potentials between the same components were similar to those between the different components in the liquid mixtures $CO_2/CH_3OCH_3$ and $CO_2/CH_3COCH_3$.

• Journal of Power System Engineering
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• v.20 no.4
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• pp.69-74
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• 2016

Recently, in order to meet the stricter emission regulations, the proportion of after-treatments for vehicle and vessel is increasing gradually. The purpose of this study is to investigate the de-$CH_4$ characteristics of NGOC in front of proposed combined system according to additive catalyst and support ratio. In the case of Pd addition, the de-$CH_4$ performance of 2Pt-2Pd-3MgO/$Al_2O_3$ NGOC was improved by approximately 10 to 20% for the HC components. The de-$CH_4$ performance of 2Pt-2Pd-3Cr-3MgO/$Al_2O_3$ NGOC was higher compared to five kinds of NGOC catalysts, because Cr particle was smaller and dispersion of Pd was increased. The NGOC(Zeolite:$Al_2O_3$(80%:20%)｝catalyst according to support ratio, was improved performance at low temperature region on CO and NO conversion rate.

• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.565-578
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• 1992

It has been suggested that Hg$^{2+}$-promoted reaction of a series of cis-[Co(en)$_2$(L)Cl]$^{2+}$ (en = 1,2-diaminoethane) with L = NH$_3$, NH$_2$CH$_3$, glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN proceeds by dissociative interchange(I$_d$) mechanism from kinetic data, circular dichroism spectra, analyses of products, and the values of m(Grunwald-Winstein plot) using Y (solvent ionizing power) in aqueous solution and in mixed aqueous-organic solvent. It has been found that chloride replacement by water (aquation) for the series with L = NH$_3$ and NH$_2$CH$_3$ and chelation of ligand L to Co(Ⅲ) for the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN occurs, respectively. The rate constants on Hg$^{2+}$-induced reaction of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were increased with increasing the contents of ethanol in mixed water-ethanol solvents. In mixed water-30${\%}$ organic solvents, the rate constants of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ have also been measured in the order 30${\%}$ 2-propanol-water > 30${\%}$ ethanol-water > water. However, the rate constants of cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were reversed. The rate constants of the series with L= NH$_3$ and NH$_2$CH$_3$ were related to ligand field parameter (${\Delta}$), but those of the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, NH$_2$CH$_2$CN were not. The reaction between the series and Hg2+ in aqueous media containing NO$_3^-$ has been investigated. The results for the reaction do not alter the mechanism, but the rate only was altered.