• Journal of the Korean Chemical Society
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• v.29 no.1
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• pp.45-51
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• 1985

Rate constants and activation parameters for the methanolysis of t-butyl halide (t-BuCl, t-BuBr, t-BuI) in various MeOH-DMSO mixtures were measured by conductometric method. Taft's solvatochromic parameters, such as polarity-polarizability(SPP's), ${\pi}^{\ast}$, hydrogen bond donor (HBD) acidity, ${\alpha}$, and hydrogen bond acceptor (HBA) basicity, ${\beta}$ of the solvents, were determined by the so called solvatochromic method using five indicators. The variation of methanolysis rate with the solvent composition was discussed on the basis of the activation parameters and the correlation of the rates with the solvatochromic parameters. It is concluded that the polarity-polarizability, HBD acidity and HBA basicity of the mixtures had an effect on the ionization of t-butyl halide cooperatively, also that the specific interaction between the leaving groups and the solvents, such as ion-dipole and hydrogen bond acceptor-donor interaction, is the most important factor of solvent effects on the stabilization of transition states.

• Bulletin of the Korean Chemical Society
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• v.23 no.12
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• pp.1754-1758
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• 2002

Tetrathiafulvalene(TTF) reacts with $PdCl_2,Pd(NO_3)_2$ and $Pd(hfacac)_2$(hexafluoroacetylacetonate) in ethanol to give $(TTF)_{1.5}PdCl_2$ (1a), $(TTF)_3Pd(NO_3)_2$ (1b) and $(TTF)_4Pd(hfacas)_2$ nd (1c), respectively. $PdCl(TCNQ)_{2.5}{\cdot}CH_3OH(2a)$was obtained from the reaction of $PdCl_2$ with LiTCNQ in methanol via the partial replacement of $Cl^-$ in $PdCl_2$ by $TCNQ^-$anion, whereas the total substitution of the labile $NO_3^-$ in $Pd(NO_3)_2$ yielded pd(TCNQ)·$CH_3OH$ (2b). $Pd(hfacac)_2(TCNQ)_2\cdot3CH_3OH$ (2c) was obtained from $Pd(hfacac)_2$ and LiTCNQ in methanol. The prepared compounds were characterized by spectroscopic (IR, UV, XPS) methods and magnetic (EPR, magnetic susceptibility) studies. The powdered electrical conductivities (${\sigma}_{rt}$) of the prepared compounds at room temperature were about~$10^{-7}S{\cdot}cm^{-1}$. The effective magnetic moments were lass than the spin-only value of one unpaired electron and no EPR signals from Pd metal ions were observed in any of the compounds, indicating that the Pd ions were diamagnetic and the magnetic moments arose from$(TTF)_n$ or $(TCNQ)_n$ moieties. The experimental evidences revealed that the charge transfer had occurred form $(TTF)_n$ moiety to the central Pd metal ion in 1a, 1b and 1c. Thus the TTF donors were ions in 2a and 2b were diamagnetic Pd(II) oxidation state. In contrast, the Pd metal ion was oxidized to Pd(IV) state in 2c as a result of an addition of $TCNQ^-$anion to $Pd(hfacac)_2$ in methanol. The oxidation states of the Pd metal ions were confirmed using the x-ray photoelectron spectroscopy.

• Bulletin of the Korean Chemical Society
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• v.30 no.5
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• pp.1157-1163
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• 2009

Complexes of Pd(btnbmtp)$Cl_2$ and Pt(btnbmptp)$Cl_2$ (btnbmtp = 2,5-bis(thiophen)-1-nonyl-3,4-bis(methylthio)- pyrrole) were prepared and their crystal structures were determined at room temperature. In the structures, the two thiophene moieties lie in cis form with an average dihedral angle of $55.26^{\circ}$ to the pyrrole frame. The luminescence properties of the free ligand and the complexes were investigated in solution and solid states. The luminescence of the compounds were not favored by substituting thiophene moieties to the pyrrole frame, compared to the unsubstituted nbmptp (nbmptp = 1-nonyl-3,4-bis(methylthio)pyrrole). In particular, thiophene substitution quenched the emission from the complexes dissolved in ,$CH_2Cl_2$ and reduced the charge transfer transitions from S atoms of the thio moieties to Pt in crystalline state, which was very characteristic of Pt(nbmptp)$Cl_2$.

• Transactions on Electrical and Electronic Materials
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• v.12 no.4
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• pp.164-168
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• 2011

Nanocrystalline cadmium sulphide (CdS) thin films were prepared using chemical bath deposition (CBD), and the structural, optical and photoconductive properties were investigated. The crystal structure of CdS thin film was studied by X-ray diffraction. The crystallite size, dislocation density and lattice constant of CBD CdS thin films were investigated. The dislocation density of CdS thin films initially decreases with increasing film thickness, and it is nearly constant over the thickness of 2,500 ${\AA}$. The dislocation density decreases with increasing the crystallite size. The Urbach energies of CdS thin films are obtained by fitting the optical absorption coefficient. The optical band gap of CdS thin films increases and finally saturates with increasing the lattice constant. The Urbach energy and optical band gap of the 2,900 A-thick CdS thin film prepared for 60 minutes are 0.24 eV and 2.83 eV, respectively. The activation energies of the 2,900 ${\AA}$-thick CdS thin film at low and high temperature regions were 14 meV and 31 meV, respectively. It is considered that these activation energies correspond to donor levels associated with shallow traps or surface states of CdS thin film. Also, the value of ${\gamma}$ was obtained from the light transfer characteristic of CdS thin film. The value of ${\gamma}$ for the 2,900 A-thick CdS thin film was 1 at 10 V, and it saturates with increasing the applied voltage.

• Journal of the Korean Chemical Society
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• v.40 no.7
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• pp.483-491
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• 1996

Dieis-Alder reaction between cyclopentadiene and 5-membered ring compounds which have exo-cyclic double bond has been studied using the PM3 method. Transition states do not show large geometrical change with the variation of dienophiles. Two isomers are possible due to the rotation of the exo-cyclic double bond of a dienophile. The reactivity for the formation of different products are explained using the FMO energy gap. The exo and endo selectivity of the reaction has been also studied from the correlation between the deformation energy and the activation barrier. Minimum energy reaction path is discussed using the Curtin-Hammett principle.

• Bulletin of the Korean Chemical Society
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• v.30 no.12
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• pp.2962-2968
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• 2009

The photodissociation dynamics of 1,2-bromochloroethane ($C_2H_4BrCl$) was investigated near 234 nm. A two-dimensional photofragment ion-imaging technique coupled with a [2+1] resonance-enhanced multiphoton ionization scheme was utilized to obtain speed and angular distributions of the nascent Br($^2P_{3/2}$) and Br${\ast}($^2P_{1/2}$) atoms. The total translational energy distributions for the Br and Br${\ast}$ channels were well characterized by Gaussian functions with average translational energies of 100 and 84 kJ/mol, respectively. The recoil anisotropies for the Br and Br${\ast}$ channels were measured to be ${\beta}$ = 0.49 ${\pm}$ 0.05 for Br and 1.55 ${\pm}$ 0.05 for Br${\ast}$. The relative quantum yield for Br${\ast}$ was found to be ${\Phi}_{Br{\ast}}$ = 0.33 ${\pm}$ 0.03. The probability of nonadiabatic transition between A' states was estimated to be 0.46. The relevant nonadiabatic dynamics is discussed in terms of interaction between potential energy surfaces in Cs symmetry.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.1958-1962
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• 2007

The title complex, Ir(H)(CO)(PEt3)2(η 2-C60) (2), has been prepared by the reaction of excess C60 (4 equiv) with a tetrairidium complex Ir4(CO)8(PEt3)4 (1) in refluxing chlorobenzene in 40% yield as green crystals. Compound 2 has been characterized by cyclic voltammetry (CV), spectroscopic methods (mass, IR, 1H and 31P NMR), and a single crystal X-ray diffraction study. The molecular structure reveals that the iridium atom of 2 is coordinated by two axial ligands of a hydrogen atom and a carbonyl group, and three equatorial ligands of two phosphorus atoms and an η 2-C60 moiety. The CV study exhibits three reversible one-electron redox waves for the successive reductions of 2, together with additional four redox waves due to free C60 reductions, which was formed by decomposition of 2 in the reduced states. The three reversible redox waves of 2 are shifted to more negative potentials by ca. 270 mV compared to free C60, reflecting both metal-to-C60 π-back-donation and the electron-donating nature of the two phosphorus ligands.

• The Journal of Korean Academy of Prosthodontics
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• v.18 no.1
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• pp.49-57
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• 1980

The adhesive mechanisms on the metal-ceramic restorations have been reported to be mechanical interlocking, chemical bonding, compressive force, and Van der Waal's force, etc. Of these, the mechanical interlocking and chemical bonding forces are thought to affect the adhesive force between Ni-Cr alloy and porcelain. This study investigates the adhesion of Ni-Cr alloy to porcelain according to surface treatment. For this purpose, the following experiments were made; The compositions of Ni-Cr alloy as cast by emission spectrograph, and the oxides produced on Ni-Cr alloy during degassing at $1850^{\circ}F$ for 30 minutes in air and in vacuum were analyzed by X-ray diffractograph. The metal phases of Ni-Cr alloy were observed according to porcelain-baking cyclic heat treatment by photo microscope and the distribution and the shift of elements of Ni-Cr alloy and porcelain and the failure phases between Ni-Cr alloy and porcelain by scanning electron microscope. The adhesive force between Ni-Cr alloy and porcelain was measured according to surface treatment with oxidization and roughening by Instron Universal Testing Machine. Results were as follows; 1. The metal phases of Ni-Cr alloy as cast and degassing state showed the enlarged and fused core, but when subjected to porcelain-baking cyclic heat treatment, showed a dendrite growing. 2. The kinds of metal oxides produced on Ni-Cr alloy during degassing were found to be NiO and $Cr_2O_3$. 3. The distribution of elements at the interface of Ni-Cr alloy and porcelain in degassing state showed demarcation line, but in roughening state, showed mechanical interlocking phase. 4. The shift of elements at the interface occurred in both states, but the shift amount was found to be larger in roughening than in degassing. 5. The adhesive force between Ni-Cr alloy and porcelain was found to be $3.45{\pm}0.93kg/mm^2$, in degassing and $3.82{\pm}0.99kg/mm^2$, in roughening. 6. The failure phase between Ni-Cr alloy and porcelain showed the mixed type failure.

• Journal of the Korean Chemical Society
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• v.28 no.5
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• pp.271-278
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• 1984

Ellipsometric and reflectance measurements were made with magneto-optically self-nulling ellipsometer on the iron surface being passivated. The passivation was induced by abruptly changing potential of the mechanically polished high purity iron from the reduction potential to the oxidation potential in basic solutions. From the differences in the optical paramates(${\Delta},\;{\psi}$) and reflectance (R) between the reduced (film-free) and oxidized (film-covered) states, the thickness(${\tau}$) and optical constants (n, k) of the film in the early stage of its formation were computed as functions of pH and time. From the computed values, it was deduced that the properties of the anodic film did not undergo a drastic change with time which would indicate a transformation of the film before effective passivity is attained, and that the film reached its stady state within a few second. The thickness of anodic film was $14\;{\sim}\;23{\AA}$. The anodic films also seemed to have small values of optical absorption coefficient. The film formed in high pH environments had thinner and denser structure than that formed in low pH.

• Journal of the Korean Chemical Society
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• v.47 no.1
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• pp.67-71
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• 2003

The present study examined the inquiry type, process, and context of activities presented in the matter field of the 7th grade science textbook based on the 7th curriculum. It was to investigate for educational suggestions in instruction and development of science textbook. Three units of ‘three states of matter', ‘motion of molecule', ‘the state change and energy' were analyzed. The result indicated that the types, processes and skills, and context of inquiry were not balanced, and learners should be educated with complementary inquiry activities. It is proposed that the inquiry activities presented in science textbooks be examined, and the framework to evaluate inquiry activities be reflected on the standard of science textbook authorization for development of the science textbook to accord with aims and objectives of curriculum.