• Title/Summary/Keyword: Chemical bonding state

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Kinetic Studies on the Reaction of 4-Substituted-2,6-dinitrochlorobenzenes with Substituted Anilines in MeOH-MeCN Mixtures (MeOH-MeCN 혼합용매계에서 4-치환-2,6-이니트로 염화벤젠과 아닐린 치환체와의 반응에 대한 속도론적 연구)

  • Dae-Ho Kang;In-Sun Koo;Jong Gun Lee;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.29 no.6
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    • pp.565-574
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    • 1985
  • The rates of reaction between 4-substituted-2,6-dinitrochlorobenzenes with para-substituted anilines in methanol-acetonitrile mixtures were measured by conductometry. It was observed that the rate constant increases in the order of X = 4-$NO_2 {\gg}4-CN {\gg}4- CF_3$, where X is a substituent in the substrate. The rate constant also increases in the order of Y = p-O$CH_3{\gg}p- CH_3{\gg}H {\gg}p-Cl{\gg}m- NO_2$, where Y is a substituent in the aniline ring. Kinetic studies in the methanol-acetonitrile solvent system with various nucleophiles showed that the N-C bond forming step is making a great contribution to the overall second order rate constant. The electrophilic catalysis by methanol probably consists of the hydrogen bonding between alcoholic hydrogen and leaving chloride in the transition state. The nucleophilic catalysis by methanol may be ascribed to the formation of hydrogen bonds between alcoholic oxygen and hydrogens of amines in the transition state. All these experimental facts are supporting the operation of $S_N$Ar machanism with the second step being the rate determining. This mechanism can be successfully fitted to the PES model.

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An Analysis of Inquiry Activities in Chemistry II Textbook by Using 3-Dimensional Analysis Framework (3차원 분석틀을 이용한 화학II 교과서의 탐구활동 분석)

  • Seok Hee Lee;Yong Keun Kim;Seong Bae Moon
    • Journal of the Korean Chemical Society
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    • v.47 no.4
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    • pp.391-400
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    • 2003
  • This study was performed the analysis of seven kinds of the hight school chemistry II textbooks based on the 6th curriculum. Particularly, inquiry activity part was analyzed by the three dimension framework which consists of inquiry content dimension, inquiry process dimension and inquiry context dimension. In the analysis of the inquiry content dimension of inquiry activities, the total number of themes in seven kinds of textbook was 212. And the number of inquiry activities in seven kinds of textbook was diverse: A textbook had 28, B textbook 25, C textbook 31, D textbook 35, E textbook 31, F textbook 29 and G textbook 33. As for the avaerage number of inquiry activities of each chapter, chapter I "Material Science" is 3.00(9.91${\%}$), chapter II "Atomic Structure and Periodic Table" 4.57(15.1${\%}$), chapter III "Chemical Bonding and Compound" 6.86(22.6${\%}$), chapter IV "State of Matter and Solution" 7.00(23.1${\%}$), chapter V "Chemical Reaction" 8.86(29.2${\%}$). For the analysis of inquiry process dimension, it follows in the order of 'observation and measuring (66.7${\%}$)', 'Interpreting data and formulating generalizations (26.5${\%}$)', 'seeing a problem and seeking ways to solve it (4.1%)', and 'building, testing and revising the theoretical model (2.7${\%}$)'. As for the analysis of the inquiry context dimension, the scientific context occupied 90.5${\%}$, the individual context 4.3${\%}$, the social context 0.9${\%}$, and the technical context 4.3${\%}$. It shows that the proportion of STS(Science-Technology-Society) related contents in inquiry activities was only 9.5${\%}$.

Structure and chemical durability of borosilicate glass-ceramics containing EAF dust (EAF dust가 포함된 붕규산염계 결정화 유리의 구조 및 화학적 내구성)

  • Ahn, Y.S.;Kang, S.G.
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.17 no.2
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    • pp.82-89
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    • 2007
  • Glass-ceramics were fabricated by heat-treating a glass at $700^{\circ}C$/10hr which was obtained by melting a glass frit mixed with $40{\sim}80 wt%$ EAF dust at $1300^{\circ}C$/1hr. Dependence of crystal phase and bonding state change upon a compositional change and heat treatment condition were studied and the results was connected to the toxic characterization leaching procedure (TCLP) test data to investigate a chemical durability of the specimens. Increasing dust in a glass shifted the peak around $1000cm^{-1}$ to the lower frequency which was composed of two vibration peaks for the nonbridging oxygen at $960cm^{-1}$ and the bridging oxygen at $1050{\sim}1060cm^{-1}$. Also, the $B_2O_3$ structure of boroxol ring changed to a tetrhedral-, trigonal- and di-borate with dust addition. The Fe-O peaks in the glass-ceramics were observed which is consitent with XRD results of spinel formation. The surface of glass after TCLP test was severely cracked while there was no cracks on a glass-ceramics after TCLP test so the chemical durability of the glass-ceramics is superior than that of glass. The leaching concentration of Fe for the glass-ceramics containing EAF dust 80 wt% is 1/15 times lower than that of glass. The Zn leaching concentration fur the glass-ceramics containing dust < 70 wt% was higher than that of glass but its trend was reversed for the specimen of dust content > 80 wt% which could be concluded as correlated with occurrence of willemite phase.

Molecular Conductance Switching Processes through Single Ruthenium Complex Molecules in Self-Assembled Monolayers

  • Seo, So-Hyeon;Lee, Jeong-Hyeon;Bang, Gyeong-Suk;Lee, Hyo-Yeong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.27-27
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    • 2011
  • For the design of real applicable molecular devices, current-voltage properties through molecular nanostructures such as metal-molecule-metal junctions (molecular junctions) have been studied extensively. In thiolate monolayers on the gold electrode, the chemical bonding of sulfur to gold and the van der Waals interactions between the alkyl chains of neighboring molecules are important factors in the formation of well-defined monolayers and in the control of the electron transport rate. Charge transport through the molecular junctions depends significantly on the energy levels of molecules relative to the Fermi levels of the contacts and the electronic structure of the molecule. It is important to understand the interfacial electron transport in accordance with the increased film thickness of alkyl chains that are known as an insulating layer, but are required for molecular device fabrication. Thiol-tethered RuII terpyridine complexes were synthesized for a voltage-driven molecular switch and used to understand the switch-on mechanism of the molecular switches of single metal complexes in the solid-state molecular junction in a vacuum. Electrochemical voltammetry and current-voltage (I-V) characteristics are measured to elucidate electron transport processes in the bistable conducting states of single molecular junctions of a molecular switch, Ru(II) terpyridine complexes. (1) On the basis of the Ru-centered electrochemical reaction data, the electron transport rate increases in the mixed self-assembled monolayer (SAM) of Ru(II) terpyridine complexes, indicating strong electronic coupling between the redox center and the substrate, along the molecules. (2) In a low-conducting state before switch-on, I-V characteristics are fitted to a direct tunneling model, and the estimated tunneling decay constant across the Ru(II) terpyridine complex is found to be smaller than that of alkanethiol. (3) The threshold voltages for the switch-on from low- to high-conducting states are identical, corresponding to the electron affinity of the molecules. (4) A high-conducting state after switch-on remains in the reverse voltage sweep, and a linear relationship of the current to the voltage is obtained. These results reveal electron transport paths via the redox centers of the Ru(II) terpyridine complexes, a molecular switch.

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A study of Compositional range of Ti-Si-N films for the ULSI diffusion barrier layer (ULSI 확산억제막으로 적합한 Ti-Si-N의 조성 범위에 관한 연구)

  • 박상기;강봉주;양희정;이원희;이은구;김희재;이재갑
    • Journal of the Korean Vacuum Society
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    • v.10 no.3
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    • pp.321-327
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    • 2001
  • Ti-Si-N films obtained by using RF reactive sputtering of targets with various Ti/Si ratios in a $N_2(Ar+N_2)$ gas mixture have been investigated in terms of films resistivity and diffusion barrier performance. The chemical bonding state of Si in the Ti-Si-N film which contained a higher Si content was in the form of amorphous $Si_3N_4$, producing increased film resistivity with increased $N_2$flow rate. Lowering the Si content in the deposited Ti-Si-N film favored the formation of crystalline TiN even at low $N_2$flow rates, and leads to low film resistivity. In addition increasing the N content led to Ti-Si-N films having a higher density and compressive stress, suggesting that the N content in the films appear to be one of the most important factors affecting the diffusion barrier characteristics. Consequently, we proposed the optimum composition in the range of 29~49 at.% of Ti, 6~20 at.% of Si, and 45~55 at.% of N for the Ti-Si-N films having both low resistivity and excellent diffusion barrier performance.

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An Experimental Study on Depositional Environments and Consolidation Properties of Shihwa Deposits (시화지역 퇴적층의 퇴적환경과 압밀특성에 관한 연구)

  • 원정윤;장병욱;김동범;손영환
    • Journal of the Korean Geotechnical Society
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    • v.20 no.5
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    • pp.49-58
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    • 2004
  • Consolidation properties of Shihwa deposits were analysed by means of depositional environments. Depositional environments including particle size distributions, sediment structures, geochemical properties, porewater chemistries and carbon age dating were analysed using undisturbed samples retrieved successively from a boring hole in the study area. Laboratory oedometer tests and anisotropic consolidated triaxial tests (CKoUC) for undisturbed samples were performed to examine the overconsolidation phenomena. Based on the results of analysis of depositional environments, it was found that the upper silt/clay mixed layer was deposited under marine condition while underlying sand and clay layers were deposited under fluvial condition. Planar laminated structures of silts and clays were dominant in marine deposits. Although there was no clear evidences that geological erosion had occurred in marine deposits, overconsolidation ratios of the upper marine samples were greater than unity Stress Paths of the upper marine samples behaved similarly to those of normally consolidated clays. Data plotted in stress state charts showed that the marine deposits were normally consolidated in geological meaning. These apparent overconsolidation of the marine deposits can be explained by the structures i.e. chemical bonding due to the difference of the rate of deposition, not by geological erosions and ground water fluctuations.

Low Temperature Deposition a-SiNx:H Using ICP Source (ICP Source를 이용한 저온 증착 a-SiNx:H 특성 평가)

  • Kang, Sung-Chil;Lee, Dong-Hyeok;So, Hyun-Wook;Jang, Jin-Nyoung;Hong, Mun-Pyo;Kwon, Kwang-Ho
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.24 no.7
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    • pp.532-536
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    • 2011
  • The silicon nitride films were prepared by chemical vapor deposition using inductively coupled plasma. During the deposition, the substrate was heated at $150^{\circ}C$ and power 1,000 W. To evolution low temperature manufacture, we have studied the role of source gases, $SiH_4$, $NH_3$, $N_2$, and $H_2$, to produce Si-N and N-H bond in a-SiNx:H film growth. $SiH_4$, $NH_3$, and $N_2$ flow rate fixed at 100, 10, and 10 sccm, $H_2$ flow rate varied from 0 to 10 sccm by small scale. To get the electrical characteristics, we makes MIM structure, and analysis surface bonding state. Experimental data show that Si-N and N-H bond is increased and hence electrical characteristics is showed 3 MV/cm breakdown-voltage, and leakage-current $10^{-7}\;A/cm^2$.

Morphology-dependent Nanocatalysis: Rod-shaped Oxides

  • Shen, Wenjie
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.130-131
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    • 2013
  • Nanostructured oxides are widely used in heterogeneous catalysis where their catalytic properties are closely associated with the size and morphology at nanometer level. The effect of particle size has been well decumented in the past two decades, but the shape of the nanoparticles has rarely been concerned. Here we illustrate that the redox and acidic-basic properties of oxides are largely dependent on their shapes by taking $Co_3O_4$, $Fe_2O_3$, $CeO_2$ and $La_2O_3$ nanorods as typical examples. The catalytic activities of these rod-shaped oxides are mainly governed by the nature of the exposed crystal planes. For instance, the predominant presence of {110} planes which are rich in active $Co^{3+}$ on $Co_3O_4$ nanorods led to a much higher activity for CO oxidation than the nanoparticles that mainly exposed the {111} planes. The simultaneous exposure of iron and oxygen ions on the surface of $Fe_2O_3$ nanorods have significantly enhanced the adsorption and activation of NO and thereby promoted the efficiency of DeNOx process. Moreover, the exposed surface planes of these rod-shaped oxides mediated the reaction performance of the integrated metal-oxide catalysts. Au/$CeO_2$ catalysts exhibited outstanding stability under water-gas shift conditions owing to the strong bonding of gold particle on the $CeO_2$ nanorods where the formed gold-ceria interface was resistant towards sintering. Cu nanoparticles dispersed on $La_2O_3$ nanorods efficiently catalyzed transfer dehydrogenation of primary aliphatic alcohols based on the uniue role of the exposed {110} planes on the support. Morphology control at nanometer level allows preferential exposure of the catalytically active sites, providing a new stragegy for the design of highly efficient nanostructured catalysts.

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Functional Polythiophene Bearing Hydroxyethyl Groups and Their Derivatives

  • Kim Hyun-Chul;Kim Jong-Seong;Baek Sung-Sik;Ree Moon-Hor
    • Macromolecular Research
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    • v.14 no.2
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    • pp.173-178
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    • 2006
  • Poly(3-(2-hydroxyethyl)thiophene) (P3HET) was synthesized using oxidative coupling polymerization that involved the protecting and deprotecting of hydroxyl groups but not the chlorine substitution or oxidative decomposition of the hydroxyl groups. The resulting P3HET exhibited good solubility in aprotic solvents, in contrast to the insoluble polymer product synthesized directly from the monomer, 3-(2-hydroxyethyl)thiophene (3HET). P3HET had low conductivity due to the strong hydrogen bonding of its hydroxyl groups. The ester-functionalized poly(3-(2-acetoxyethyl)thiophene) and poly(3-(4-pentylbenzoateethyl)thiophene) were also prepared with reasonably high molecular weights in order to examine how this functionalization modified the physical and chemical properties of P3HET. These polymers exhibited better solubility in common solvents and higher conductivity than P3HET. All these polymers exhibited bathochromic shifts of their film state absorption maxima with respect to those found in the UV-visible spectra of their solution phases. The extent of the bathochromic shift was found to vary with the lengths of the side chains of the ester-functionalized polymers.

Monolayer Characteristics of Bilayer Forming Phosphate Amphiphiles (이분자막 형성능을 가지는 인산형 양친매성 화합물의 단분자막 특성)

  • ;Kunitake, T.
    • Membrane Journal
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    • v.5 no.2
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    • pp.89-96
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    • 1995
  • The monolayer characteristics of phosphate amphiphiles with azobenzene at air/water interface were studied by the measurment of $\pi-A$ curves and absorption spectra. Immediately after being spread on the water surface, these amphiphiles having strong intermolecular hydrogen bonding interactions showed the typical absorption spectra which resulted from domain formation. But the aggregated domains could be controlled by changing the subphase conditions (adding bulky salt and rasing pH). Addition of metal ions in subphase changes the molecular orientation of monolayer. As the metal ion charge increases ($1\leq2$ < 3 < 4 valence), the absorption maximum (310nm) of the amphiphile with azobenzene shifts to a longer wavelength (350nm) which means that the orientation of the amphiphile is tilted. These results suggest that the molecular orientation, and furthermore the aggregation state of monolayer can be possibly controlled by the interaction of metal ions with different charge types.

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