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Matrix Infrared Spectra and DFT Computations of CH2CNH and CH2NCH Produced from CH3CN by Laser-Ablation Plume Radiation

  • Cho, Han-Gook
    • Bulletin of the Korean Chemical Society
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    • v.34 no.5
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    • pp.1361-1365
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    • 2013
  • The smallest ketenimine and hydrogen cyanide N-methylide ($CH_2CNH$ and $CH_2NCH$) are provided from the argon/acetonitrile matrix samples exposed to radiation from laser ablation of transition-metals. New infrared bands are observed in addition to better determination of the vibrational characteristics for the previously reported bands, and the $^{13}C$ substituted isotopomers ($^{13}{CH_2}^{13}CNH$ and $^{13}CH_2N^{13}CH$) are also generated. Density functional frequency calculations and the D and $^{13}C$ isotopic shifts substantiate the vibrational assignments. $CH_2CNH$ is probably produced through single-step conversion of $CH_3CN$, whereas $CH_2NCH$ through two-step conversion via 2H-azirine. Inter-conversions between these two products evidently do not occur during photolysis and annealing.

Gas Sensing Characteristics of Nano Sized SnO2 Sensors for Various Co and Ni Concentration (Co, Ni 농도 변화에 따른 나노 SnO2 센서의 감응 특성)

  • Lee, Ji-Young;Yu, Yoon-Sic;Yu, Il
    • Korean Journal of Materials Research
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    • v.21 no.10
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    • pp.546-549
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    • 2011
  • Nano-sized $SnO_2$ thick films were prepared by a screen-printing method onto $Al_2O_3$ substrates. The sensing characteristics were investigated by measuring the electrical resistance of each sensor in a test box as a function of the detection gas. The nano-sized $SnO_2$ thick film sensors were treated in a $N_2$ atmosphere. The structural properties of the nano $SnO_2$with a rutile structure according to XRD showed a (110) dominant $SnO_2$ peak. The particle size of $SnO_2$:Ni nano powders at Ni 8 wt% was about 45 nm, and the $SnO_2$ particles were found to contain many pores according to the SEM analysis. The sensitivity of the nano $SnO_2$-based sensors was measured for 5 ppm $CH_4$ gas and $CH_3CH_2CH_3$ gas at room temperature by comparing the resistance in air with that in the target gases. The results showed that the best sensitivity of $SnO_2$:Ni and $SnO_2$:Co sensors for $CH_4$ gas and $CH_3CH_2CH_3$ gas at room temperature was observed in $SnO_2$:Ni sensors doped with 8 wt% Ni. The response time of the $SnO_2$:Ni gas sensors was 10 seconds and recovery time was 15 seconds for the $CH_4$ and $CH_3CH_2CH_3$ gases.

Catalytic Reactions of 3-Phenyl-2-propen-1-ol with Perchloratocarbonylbis (triphenylphosphine) rhodium (I)$^\dag$

  • Park, Jeong-Han;Chin, Chong-Shik
    • Bulletin of the Korean Chemical Society
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    • v.8 no.4
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    • pp.324-328
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    • 1987
  • Reaction of Rh $(ClO_4)(CO)(PPh_3)_2$ (1) with trans-$C_6H_5CH = CHCH_2OH$ (2) produces a new cationic rhodium(Ⅰ) complex, $[Rh(trans-C_6H_5CH = CHCHO)(CO)(PPh_3)_2]ClO_4$ (3) where 2 is coordinated through the oxygen atom but not through the olefinic group. At room temperature under nitrogen, complex 1 catalyzes dehydrogenation, hydrogenolysis, and isomerization of 2 to give $trans-C_6H_5CH$ = CHCHO (4), trans-$C_6H_5CH = CHCH_3$ (5) and $C_6H_5CH_2CH_2CHO$ (6), respectively, and oligomerization of 2 whereas under hydrogen, complex 1 catalyzes hydrogenation of 2 to give $C_6H_5CH_2CH_2CH_2OH$ (7) and hydrogenolysis of 2 to 5 which is further hydrogenated to $C_6H_5CH_2CH_2CH_3$ (8). The dehydrogenation and hydrogenolysis of 2 with 1 suggest an interaction between the rhodium and the oxygen atom of 2, whereas the isomerization and hydrogenation of 2 with 1 indicate an interaction between the rhodium and the olefinic system of 2.

Electrochemical Properties of Diiron Complexes wish Conjugated Chains (공액 사슬을 갖는 철 화합물의 전기화학적 특성)

  • ;Micheal b. Sponsler
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.15 no.6
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    • pp.511-517
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    • 2002
  • The complex 1 $([Cp*Fe(CO)_2]_2-(\mu-CH=CH-CH=CH))$ which have butadiene as a bridge were synthesized from $Cp*(CO)_2FeK$ and cis-3,4-dichlorocyclobutene. The derivatives of complex 1 where one or two carbonyl groups are replaced by phosphine ligands have been prepared by photochemical substitution. The new derivatives $([Cp*Fe(L)_2]_2-(\mu-CH=CH-CH=CH))$ where L = $(Ph_2PCH_2CH_2PPh_2)$ and $([Cp*Fe(CO)(L)]_2-(\mu-CH=CH-CH=CH))$ where L : $PPh_3$ have been characterized from $^^1H-$, $^^13C-$,$^^31P-NMR$ and elemental analysis. Obtained complexes have been studied in electrochemical experiment and UV/VIS-near-IR. The mixed-valence radical cation forms of complex 2, 3 species were found to be delocalized as the Class III. Based on the separation of the waves ($\triangle E$ : 0.470 ~ 0.605 V), the efficiency of electronic communication between two metal centers of cation species leading to stabilization relative to neutral species. The phosphine-substitute complexes (2, 3) displays two reversible oxidation waves and oxidation state of metal centers-dependent color change, electrochromism, was observed from yellow to orange and deep blue in methylene chloride.

The Influence of CH3Cl on CH4/CH3Cl/O2/N2 Premixed Flames Under the O2 Enrichment (산소부화 조건인 CH4/CH3Cl/O2/N2 예혼합 화염에서 CH3Cl의 영향)

  • Shin Sung Su;Lee Ki Yong
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.29 no.2 s.233
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    • pp.255-262
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    • 2005
  • A comprehensive experimental and numerical study has been conducted to understand the influence of $CH_{3}Cl$ addition on $CH_4/O_2/N_2$ premixed flames under the oxygen enrichment. The laminar flame speeds of $CH_4/CH_{3}Cl/O_2/N_2$ premixed flames at room temperature and atmospheric pressure are experimentally measured using Bunsen nozzle flame technique, varying the amount of $CH_{3}Cl$ in the fuel, the equivalence ratio of the unburned mixture, and the level of the oxygen enrichment. The flame speeds predicted by a detailed chemical kinetic mechanism employed are found to be in excellent agreement with those deduced from experiments. Even though the molar amount of $CH_{3}Cl$ in a methane flame is increased, temperature at the postflame is not significantly varied, but the calculated heat release rate and emission index of NO are largely decreased for the oxygen enhanced flame. The function of $CH_{3}Cl$ as inhibitor on hydrocarbon flames becomes weakened as the level of the oxygen enrichment is increased from 0.21 to 0.5.

The Influence of $CH_{3}Cl$ on $CH_{4}/CH_{3}Cl/O_{2}/N_{2}$ Premixed Flames under the Oxygen Enrichment (산소부화 조건인 $CH_{4}/CH_{3}Cl/O_{2}/N_{2}$ 예혼합 화염에서 $CH_{3}Cl$의 영향)

  • Shin, Sung-Su;Lee, Ki-Yong
    • Proceedings of the KSME Conference
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    • 2004.11a
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    • pp.1128-1133
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    • 2004
  • A comprehensive experimental and numerical study has been conducted to understand the influence of $CH_{3}Cl$ addition on $CH_{4}/O_{2}/N_{2}$ premixed flames under the oxygen enrichment. The laminar flame speeds of $CH_{4}/CH_{3}Cl/O_{2}/N_{2}$ premixed flames at room temperature and atmospheric pressure are experimentally measured using Bunsen nozzle flame technique, varying the amount of $CH_{3}Cl$ in the fuel, the equivalence ratio of the unburned mixture, and the level of the oxygen enrichment. The flame speeds predicted by a detailed chemical kinetic mechanism employed are found to be in excellent agreement with those deduced from experiments. As $CH_{3}Cl$ addition is increased temperature at the postflame is not almost varied but the heat release rate and $EI_{NO}$ are decreased. The function of $CH_{3}Cl$ as inhibitor on hydrocarbon flames becomes weakened as the level of the oxygen enrichment is increased from 0.21 to 0.5.

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Reaction of the Fe(II) Macrocyclic Complexes with Dioxygen : Preparation of New Unsaturated Ring Systems by Oxidative Dehydrogenation Reactions of Fe(II) Macrocyclic Ligands (이가철 거대고리 리간드의 착화합물과 산소 분자간의 반응 : 이가철 거대고리 리간드 착화합물의 산화성 탈수소 반응에 의한 새로운 불포화 고리계의 합성)

  • Myunghyun Paik;Shin-Geol Kang;Kyu Whan Woo
    • Journal of the Korean Chemical Society
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    • v.28 no.6
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    • pp.384-392
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    • 1984
  • Reaction of the Fe(II) complex of a fully saturated tetradentate macrocyclic ligand [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$, where [14]ane$N_4$ represents 1,4,8,11-tetraazacyclotetradecane, with $O_2$ has been investigated in acetonitrile solutions. [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$ reacts with oxygen to yield low spin Fe(III) species, [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$, which undergoes metal ion assisted oxidative dehydrogenation of the macrocyclic ligand to produce low spin Fe(II) complex, [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$. The macrocyclic ligand in [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$ is highly unsaturated and its double bonds are conjugated. [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ and [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$ are isolated as the intermediates of the reaction. The Fe(II) complexes involved in this oxidative dehydrogenation reaction react with carbon monoxide to give respective carbon monoxide derivatives, [FeL$(CH_3CN)(CO)]^{2+}$ (where L = macrocyclic ligand). The values of $v_{CO}$ of [FeL$(CH_3CN)(CO)]^{2+}$, and the electrochemical oxidation potentials of Fe(II) ${\to}$ Fe(III) and the qualitative stability toward air-oxidation for [FeL(CH$_3CN_2)^{2+}$ increase as the degree of unsaturation of the macrocyclic ligands increase.

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Studies on the Distribution Coefficient of the Primary, Secondary, Tertiary Amine and Quaternary Ammonium-methylorange Salts

  • Kim, Bak-Kwang
    • YAKHAK HOEJI
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    • v.18 no.3
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    • pp.183-189
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    • 1974
  • Distribution coefficients between nitrobanzene solution and deionized water, show a straight line when the number of alkyl radicals against the logarithm of distribution coefficient of the salts was plotted. After extracting salts of the indicator and the cationic surfactants with organic solvents, and employing the colorimetric method was used. A calculation method of distribution coefficients of the salts in the organic solvent has been suggested and it could be used for the extraction equilibrium of the primary amine, $CH_{3}(CH_2)_{n}NH_3^+$ secondary amine, $CH_{3}(CH_2)_{n}NH_{2}(CH_3)^+$, tertiary amine $CH_{3}(CH_2)_{n}NH(CH_3)_2^+$ and quaternary ammonium, $CH_{3}(CH_2)_{n}N(CH_3)_3^+$MO$^-$salts, (n=3,5,7,11).

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optical emission spectra of microwave plasma (마이크로파 플라즈마의 광방출 스펙트럼)

  • Park, Sang-Hyun;Gu, Hyo-Keun;Sim, Jung-Bong;Kim, Kyoung-Hwan;Park, Jae-Yoon;Lee, Duck-Chool
    • Proceedings of the KIEE Conference
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    • 1998.11c
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    • pp.895-897
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    • 1998
  • The optical spectra of microwave plasma by four kinds of gases($N_2$, $N_2-CH_4$, $H_{2}-CH_{4}$ and Air-$CH_4$) have been measured for investigating 388.4[nm] peak which has the same intensity as $H_{\alpha}$(656.4[nm]) peak. A 388.4[nm] peak by $N_2$ plasma, $N_{2}-CH_{4}$ plasma and Air-$CH_4$ plasma may be CN peak because it is with 337.1, 357.8 and 316.0[nm] peaks by $N_2$. And a 388.4[nm] peak by $H_{2}-CH_{4}$ plasma without by $N_2$ 337.1, 357.8 and 316.0[nm] peaks may be CH peak. In the investigation results for optical spectra by $H_{2}-CH_{4}$ plasma and $H_{2}-CH_{4}-O_{2}$ plasma, the density of hydrogen atom was increased because oxygen decompose hydrogen molecules in $H_{2}-CH_{4}$ plasma with oxygen. These hydrogen atom decompose $CH_4$ and increase CH radical. And the crystalline of deposited diamond was good and the growth rate increased.

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Studies of Oxo-Nitrosyl Complexes(Ⅱ) Synthesis and Properties of Tungsten Oxo-Nitrosyl Complexes with Butylamidoxime Derivatives (산소-니트로실 착물의 연구 (제2보) 부틸아미드옥심 유도체의 텅스텐 산소-니트로실 착물의 합성과 특성)

  • Roh, Soo Gyun;Oh, Sang Oh
    • Journal of the Korean Chemical Society
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    • v.39 no.11
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    • pp.856-862
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    • 1995
  • The tungsten oxo-nitrosyl complexes (n-Bu4N)2[W5O12(NO)2{RC(NH2)NHO}2{RC(NH)NO}2] (R=(CH3)2CH, CH3CH2CH2, CH3SCH2) have been synthesized by the reactions of polyoxotungsten complex (n-Bu4N)2[W6O19] and tungsten dinitrosyl monomeric complex [W(NO)2(acac)(CH3CN)2](BF4) with butylamidoxime derivatives. The prepared complexes have been characterized by elemental analysis, infrared, UV-visible, 1H NMR and 13C NMR spectroscopy. The pentanuclear species was formed by the interaction of the electron-withdrawing {W(NO)2}2+ unit between the two dinuclear tungsten {W2O5}2+ cores. We can estimate to exist large proton interactions viewed from the four doublet in 1H NMR spectrum of (n-Bu4N)2[W5O12(NO)2{(CH3)2CHC(NH2)NHO}2{(CH3)2CHC(NH)NO}2]. We also drew informations of the two different coordination mode and symmetry of the complexes because two ligands appear in 13C NMR spectra instead of four. The {W(NO)2}2+ unit has been cis-form and C2v symmetry in geometric structure.

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