• Title/Summary/Keyword: $C_{14}H_{14}O_4N_2$

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Synthesis of Binuclear Bismacrocyclic Iron(II) Complex by the Aerobic Oxidation of Iron(II) Complex of 1,4,8,11-Tetraazacyclotetradecane

  • Myunghyun Paik Suh;Gee-Yeon Kong;Il-Soon Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.439-444
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    • 1993
  • The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

The Crystal Structure of Ethylenediamine Dihydrochloride $ClH{\cdot}H_2N{\cdot}CH_2{\cdot}CH_2{\cdot}NH_2{\cdot}HCl$ (Ethylenediamine 鹽酸鹽의 結晶構造)

  • Chung Hoe Koo;Moon Il Kim;Chung Soo Yoo
    • Journal of the Korean Chemical Society
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    • v.7 no.4
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    • pp.293-298
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    • 1963
  • The crystal structure of ethylenediamine dihydrochloride has been determined by the two-dimensional Patterson methods and refined by two-dimensional Fourier syntheses. The unit cell dimensions are a = 4.44${\pm}$0.02, b = 6.88${\pm}$0.02, c = 9.97${\pm}$0.02 ${\AA}$, ${\beta}$ = 92${\pm}$$1^{\circ}$. The space group is $P2_1_{/c}$. The carbon and nitrogen atoms in the ethylenediamine itself lie on one plane and its structure has a trans-form with a centre of symmetry in it, and C-C distance of 1.54 ${\AA}$, C-N distance of 1.48${\AA}$ and C-C-N bond angle of $109.07^{\circ}$. The molecules are linked by N-H${\cdots}$Cl hydrogen bonds with distance of 3.14, 3.16 and 3.22 ${\AA}$ forming three dimensional network. The values of reliability factor for F(okl), F(hol) and F(hko) are 0.11, 0.10 and 0.09 respectively.

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The Investigation of Detonation Characteristics of Ethylene Oxide Mixture by Using Incident Shock Tube Technique (입사 충격파관을 이용한 에틸렌 옥사이드 혼합물의 데토네이션 특성연구)

  • Moon, J.H.;Chung, J.D.;Kang, J.G.
    • Transactions of the Korean Society of Automotive Engineers
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    • v.2 no.5
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    • pp.121-134
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    • 1994
  • Shock tube investigation of ethylene oxide-$0_{2}-N_{2}$ mixture have been performed to reveal detonation characteristics of the mixture in terms of detonation pressure and speed. Theoretical calculation of thermodynamic parameters at the Chapmann-Jouguet detonation of the mixture has been also performed. A comparision of the observed results with the calculated ones can lead us to predict the detonation parameters of ethylene oxide in an artificial air. In addition, we have observed ignition delay times of ethylene oxide mixtures. The best fit of the observed delay times to Arrhenius gas kinetic relation gives : ${\tau}=10^{-144}{e{xp}}(E_a/RT)[C_{2}H_{4}O]^{-4.8}[O_{2}]^{-12.4}[N_{2}]^{-14.1}$ $E_a=3.67kcal/mole$ The observed activation energy is markedly reduced, compared with the case of ethylene oxide diluted in Ar. It could be due to the factor that $N_2$ play a role as detonation promoter yielding very reactive NOx radicals.

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A Study on the Thermal Characteristics of Waste Organic Sludges Generated from the Industrial Complex -Paper and Beverage Manufacturing Industries- (산업단지에서 배출되는 폐 유기성 슬러지의 열적 특성 -제지업 및 음식료업을 중심으로-)

  • Shon, Byung-Hyun;Lee, Joo-Ho;Jung, Moon-Hun;Kim, Min-Choul;Ko, Ju-Hyun;Park, Hung-Suck;Lee, Gang-Woo
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.9 no.5
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    • pp.1359-1367
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    • 2008
  • We analyzed the physical and chemical properties such as proximate analysis, ultimate analysis, heating values, thermogravimetric analysis, and combustion test for the organic sludges generated from paper and beverage manufacturing industries in the industrial complex. The average water and combustible content of the organic sludges from paper and beverage manufacturing industries were 66.07% and 14.67%, 54.98% and 26.77%, respectively. From the ultimate analysis of the organic sludges, C, H, O, N, and S compositions were 21.75%, 3.42%, 32.70%, 0.63%, and 0.30%, respectively. For beverage manufacturing industries, C, H, O, N, and S compositions were 39.88%, 4.28%, 23.20%. 2.65%, and 0.35%, respectively. According to the results of investigating the lower heating values by Dulong's equation, 1 sludge(T company) was on the range of over 2,000 kcal/kg. This sludge could be directly applied to industries which try to use the energy by direct incineration. From the TGA test, the minimum combustion temperature of A company's sludge was about $700^{\circ}C$ for direct use for energy and that of 3 sludges(C, I, and T company) were at least over $800^{\circ}C$.

Synthesis and Characterization of Dinuclear Ni(II) Complexes with Tetraazadiphenol Macrocycle Bearing Cyclohexanes

  • Kim, Ki-Ju;Jung, Duk-Sang;Kim, Duk-Soo;Choi, Chi-Kyu;Park, Ki-Min;Byun, Jong-Chul
    • Bulletin of the Korean Chemical Society
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    • v.27 no.11
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    • pp.1747-1751
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    • 2006
  • The dinuclear tetraazadiphenol macrocyclic nickel(II) complexes [$Ni_2$([20]-DCHDC)]$Cl_2$ (I), [$Ni_2$([20]-DCHDC)]$(ClO_4)_2{\cdot}2CH_3CN $ (II(b)) and [$Ni_2$([20]-DCHDC)$(NCS)_2$] (III) {$H_2$[20]-DCHDC = 14,29-dimethyl-3,10,18,25-tetraazapentacyclo-[25,3,1,$0^{4,9}$,$1^{12,16}$,$0^{19,24}$]ditriacontane-2,10,12,14,16(32),17,27(31), 28,30-decane-31,32-diol} have been synthesized by self-assembly and characterized by elemental analyses, conductances, FT-IR and FAB-MS spectra, and single crystal X-ray diffraction. The crystal structure of II(b) is determined. It crystallizes in the monoclinic space group P2(1)/c. The coordination geometries around Ni(II) ions in I and II(b) are identical and square planes. In complex III each Ni(II) ion is coordinated to $N_2O_2$ plane from the macrocycle and N atoms of NCS- ions occupying the axial positions, forming a square pyramidal geometry. The nonbonded Ni…Ni intermetallic separation in the complex II(b) is 2.8078(10) $\AA$. The FAB mass spectra of I, II and III display major fragments at m/z 635.1, 699.4 and 662.4 corresponding to [$Ni_2$([20]-DCHDC)(Cl + 2H)]$^+$, [$Ni_2$([20]-DCHDC)$(ClO_4\;+\;2H)]^+$ and [$Ni_2$([20]-DCHDC)(NCS) + 6H]$^+$, respectively.

Preparation of $MgO-ZrO_2$ Fibers by Sol-Gel Method and Their Characterization (졸-겔법에 의한 $MgO-ZrO_2$ 섬유의 제조와 특성)

  • 황진명;은희태
    • Journal of the Korean Ceramic Society
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    • v.31 no.10
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    • pp.1147-1158
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    • 1994
  • From Zr(O-nC3H7)4-H2O-C2H5OH-HNO3 starting solutions, MgO-doped stabilized zirconia fibers with varying content of MgO (10~18 mol%) from different MgO sources were fabricated by sol-gel method. The MgO sources used are magnesium nitrate hexahydrate, magnesium acetate tetrahydrate, and magnesium ethylate. The phase transformation studies of a drawn MgO-ZrO2 fiber were carried out using X-ray diffraction, IR spectroscopy, and Raman spectroscopy. The microstructure, tensile strength, and microporosity of fibers were investigated using SEM, tensile strength test, and microporosimeter. Although various MgO sources such as magnesium nitrate, acetate, and ethylate were used, the crystallization behavior of MgO-ZrO2 fibers at different temperatures could be summarized as follows: CubiclongrightarrowMetastable TetragonallongrightarrowMonocliniclongrightarrowCoexistence of Monoclinic and CubiclongrightarrowCubic(trace of monoclinic). At 150$0^{\circ}C$, the phase transformation of MgO-ZrO2 fibers shows the following change depending on the amount of MgO[Mg(NO3)2.6H2O]: At 10 mol%, both monoclinic and cubic phase coexist, at 12 mol%, monoclinic phase decreases rapidly, and then at 14 mol%, only cubic phase remains. When the MgO-ZrO2 fibers containing 12 mol% magnesium nitrate were heated at 80$0^{\circ}C$ for 1hr, average tensile strength of fibers is 4.0 GPa at diameters of 20 to 30 ${\mu}{\textrm}{m}$. As the heat-treatment temperatures increase to 100$0^{\circ}C$ for 1 hr, tensile strength of MgO-ZrO2 fibers decreases rapidly to 0.7 GPa.

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Electrochemical Properties and Crystal Structure of $Li_{1+x}Mn_2O_4$($0\leqx\leq0.075$) Synthesized at Solid State Method (고상법에 의한 $Li_{1+x}Mn_2O_4$ ($0\leqx\leq0.075$) 의 결정구조와 전기화학적 특성)

  • 박종광;고건문;임성훈;황종선;한병성
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.14 no.5
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    • pp.383-390
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    • 2001
  • We have investigated the L $i_{1+x}$M $n_2$ $O_4$system as a cathode material for lithium rechargeable batteries. To improve the cycle performance of spinel LiM $n_2$ $O_4$ as the cathode of 4V class lithium secondary batteries, spinel phase L $i_{1+x}$M $n_2$ $O_4$(x=0, 0.025, 0.05, 0.075) was prepared at 75$0^{\circ}C$ for 48h. The preparation of L $i_{1+x}$M $n_2$ $O_4$ from L $i_2$ $O_3$ and Mn $O_2$ under air is studied. The compounds were synthesized by using solid-state reaction. Structural refinements were carried out with a Rietveld-refinement program. Electrochemical properties were examined using the Li/L $i_{1+x}$M $n_2$ $O_4$ cells. The capacity of L $i_{1+x}$M $n_2$ $O_4$ decreases with increases lithium content, while the cycle life improves. The initial discharge capacity are 118mAh/g and 116mAh/g for LiM $n_2$ $O_4$ decreases with increases lithium content, while the cycle life improves. The initial discharge capacity are 118mAh/g and 116mAh/g for LiM $n_2$ $O_4$ and L $i_{1.025}$M $n_2$ $O_4$, respectively.pectively.

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Study on the freshness change of Pacific Macheral, Hair Tail, and Alaska Pollack by the various storage conditions (고등어, 칼치, 명태의 선도변화에 관한 연구)

  • 김영희
    • Journal of the Korean Home Economics Association
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    • v.19 no.1
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    • pp.39-45
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    • 1981
  • The fishes that are mostly used in our homes such as Pacific Mackeral, hair Tail and Alaska Pollack were devided into Freezing group, Refrigerating group and Room temperature group according to storage temperature. TVB-N, TMA-N, TMA-O and pp.H. were measured in natural state, after water washing and 3% NaCl-water washing. The results are as follows: 1. Regardless of the kinds of fishes, TVB-N in room temperature showed that rottenness first appeared after 5~8 hours in raw state, 6~12 hours in water washing, and 8~12 hours in 3% NaCl-water washing. 2. Regardless of freezing and refrigeration, Pacific Mackeral became rotten after 14 days in raw state, 14~17 days in water washing and 17 days in 3% NaCl water washing. Alaska Pollack and Hair Tail showed rottenness after 8 days in raw state, 11 days in water and 3% NaCl water washing. 3. Even in hot summer days, freshness could be preserved for 10 days if fishes were freezed ($-20^{\circ}C$) or refrigerated (4~$8^{\circ}C$) after bowel excluded, washed in NaCl water and enveloped in poly-ethylene bag.

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Metalorganic Chemical Vapor Deposition of Copper Films on TiN Substrates Using Direct Liquid Injection of (hfac)Cu(vtmos) Precursor ((hfac)Cu(vtmos)의 액체분사법에 의한 TiN 기판상 구리박막의 유기금속 화학증착 특성)

  • Jun, Chi-Hoon;Kim, Youn-Tae;Kim, Dai-Ryong
    • Korean Journal of Materials Research
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    • v.9 no.12
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    • pp.1196-1204
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    • 1999
  • We have carried out copper MOCVD(metalorganic chemical vapor deposition) onto the reactive sputtered PVD-TiN and rapid thermal converted RTP-TiN substrates using direct liquid injection for effective delivery of the (hfac)Cu(vtmos) [$C_{10}H_{13}O_{5}CuF_{6}$Si: 1,1,1,5,5,5-hexafluoro-2,4- pentadionato (vinyltrimethoxysilane) copper (I)] precursor. Especially, the influences of deposition conditions and the substrate type on growth rate, crystal structure, microstructure, and electrical resistivity of copper deposits have been discussed. It is found that the film growth with 0.2ccm precursor flow rate become mass-transfer controlled up to Ar flow rate of 200sccm and pick-up rate controlled at a vaporizer above 1.0Torr reactor pressure. The surface-reaction controlled region from 155 to 225$^{\circ}C$ at 0.6Torr reactor pressure results in the apparent activation energies of 12.7~14.1kcal/mol, and above 224$^{\circ}C$ the growth rate with $H_2$ addition could be improved compared to the pure Ar carrier. The Cu/RTP-TiN structures which have high copper nucleation density in initial stage of growth show more pronounced (111) preferred orientations and lower electrical resistivities than those on PVD-TiN. The variation of electrical resistivity with substrate temperature reflects the three types of film microstructure changes, showing the lowest value for the deposit at 165$^{\circ}C$ with small grains of good contacts.

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The Studies of the Water-Vapour Transmission Rate and It's Proofness on the Various Commercial Polymer Films (상업용 고분자 필름의 투습속도 및 방습도에 관한 연구)

  • Hwan Kyu Suh;Jung Keun Lee
    • Journal of the Korean Chemical Society
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    • v.23 no.5
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    • pp.329-337
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    • 1979
  • The water-vapour transmission ratios (WVTR) of the various commercial polymer films have been investigated at the constant pressure and relative humidity (RH). Water proofnesses, the reciprocals of WVTR for the various samples, were determined using a cup device and maintaining the sample films at a constant temperature ($40{\pm}1^{\circ}C$) and a constant R. H ($90{\pm}2%$) for 24 hours. The following order of the relative proofness was observed; oriented polypropyrene (O.PP) > high density polyethylene (HDPE, Inflation) > high density polyethylene (HDPE. T-die) > casted polypropylene (C. PP) > nonoriented polyester (N. PET) > low density polyethylene (LDPE) > oriented polyester (O. PET) > rigid polyvinyl chloride (Rigid PVC) > semirigid polyvinyl chloride (Semirigid PVC) > nonrigid polyvinyl chloride (Nonrigid PVC) > oriented nylon (O. Nylon) > nonoriented nylon (N. Nylon). And water proofness order was also observed to decrease with the temperature rising; HDPE (T-die) > C. PP > O. PET > LDPE > O. Nylon. The activation energies of LDPE, HDPE (T-die), C. PP, O. PET and O.Nylon films were 12.0, 11.1, 11.4, 11.7, 14.1 kcal/mole, respectively. The WVTR's of the films were increased with the polarity of polymer and the addition of plasticizer in PVC, decreased with the increase of the film thickness and mechanical orientation. The WVTR's of the laminated films O. PP/LDPE, N.Nylon/LDPE, C.PP/LDPE were also more dependent on the film thickness than the WVTR's of the single films.

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