• Title/Summary/Keyword: 반응도(R)

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Substituent Effects on the Wallach Rearrangement of 4'-Halogenated Azoxybenzenes in Conc. Sulfuric Acid : Reaction Mechanism and Linear Free Energy Relationship (황산 수용액내에서 4'-Halogenated Azoxybenzenes의 Wallach Rearrangement 반응에 대한 치환체효과 : 반응메카니즘과 Linear Free Energy Relationship)

  • Keum Sam-Rok;Lee Hyo-Il
    • Journal of the Korean Chemical Society
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    • v.37 no.1
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    • pp.148-153
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    • 1993
  • The Wallach rearrangement of 4'-halogenated azoxybenzenes in strong sulfuric acid was reinvestigated by UV-Vis spectrophotometric method. Interestingly an excellent linearity $(logk_{obs}=-0.61\;{\sigma}_R{^+} -3.29,\;{\gamma = 0.998)$ was obtained on plotting log (rate) vs. substituent constant, ${\sigma}_R{^+}$, which is known as the Pi delocalization parameter. Thus B-H mechanism via a charged intermediate $(DC^{++})$, which can be largely stabilized by resonance, is far more favored for the Wallach rearrangement.

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Investigation on Rheological and Mechanical Properties of Propellant with Chemical Structures of HTPB Binder (HTPB 바인더의 화학적 구조에 따른 추진제의 유변학적, 기계적 특성 연구)

  • Kim, Jeong Eun;Ryu, Taeha;Hong, Myung Pyo;Lee, Hyoung Jin
    • Journal of the Korean Society of Propulsion Engineers
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    • v.21 no.1
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    • pp.84-90
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    • 2017
  • It is observed that chemical characteristics of HTPB(Hydroxyl Terminated Polybutadiene) binder such as OH index, molecular weight and functionality and so on, can be different with synthetic batch, which can affect curing reaction of binder in itself or propellant. Finally this reaction can also affect mechanical properties of propellant. And the results suggest that proper degree of curing reaction is necessary to obtain better mechanical properties of propellant.

Synergy Effects of Hybrid Catalysts on Syngas Yield of Partial Oxidation of Methane (메탄의 부분산화를 통한 합성가스 제조에서의 hybrid 촉매의 영향)

  • 오영삼;백영순;이재의;목영일
    • Journal of Energy Engineering
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    • v.8 no.1
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    • pp.34-47
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    • 1999
  • 본 연구에서는 촉매상에서 메탄의 산화시 발생되는 반응열을 이용하고 반응생성물과 미반응 메탄과의 개질반응에 의해 합성가스의 수율을 증대시키기 위하여 연소촉매와 개질촉매를 연속적으로 배치한 hybrid 촉매상에서 개질촉매에 따른 메탄의 부분산화반응의 반응 특성과 합성가스 수율에 미치는 영향을 관찰하였다. 메탄의 산화를 위해서 Pt-Rh/cordierite 촉매를 사용하였으며, 개질촉매로는 상업용 개질촉매인 R67, ICI46-1, 수성가스 전환반응촉매인 LX821 촉매와 6 wt% Ni/cordierite 촉매를 사용하였다. 실험결과 연소촉매와 개질촉매를 연속적으로 사용한 경우 메탄의 산화 과정에서 생성된 CO2 및 H2O가 미반응 메탄과의 개질반응 촉진으로 인하여 합성가스이 수율이 증가됨을 확인할 수 있었다. 이때 생성되는 합성가스의 H2/CO 몰비는 온도에 따라 감소하는 것으로 나타났으며, 80$0^{\circ}C$에서 촉매에 따라 2.2~2.8의 값을 가짐을 알 수 있었다. 개질촉매로 R67 및 Ni/cordierite 촉매를 사용하였을 경우 가장 높은 합성가스의 수율을 얻을 수 있었으며, 연소촉매와 개질촉매의 질량비는 1:1~1:2에서 가장 높은 수율의 합성가스를 얻을 수 있었다. 메탄과 산소의 몰비가 2:2에서 메탄의 전환율과 수소 수율이 가장 높게 나타났으며 메탄의 몰비 증가에 따라 감소되는 경향을 보였다.

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Physicochemical Properties and Antioxidant Activities of Maillard Reaction Products from Defatted Hydrolyzed Soybean Protein with Various Sugars (탈지대두단백 산 가수 분해물과 당의 반응에 의하여 생산된 Maillard Reaction Products의 이화학적 특성 및 항산화성)

  • Kim, Yoon-Sook;Moon, Ji-Hye;Kim, Myung-Hee;Choi, Hee-Don;Park, Yong-Kon
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.38 no.1
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    • pp.62-69
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    • 2009
  • Maillard reaction products (MRPs) were produced from aqueous solution of various sugars with defatted hydrolyzed soybean protein (DFHSP) with different temperatures and pressures. Physicochemical properties of MRPs were investigated; also, DPPH and hydroxyl radical scavenging activity and sensory properties were evaluated. MRPs from ribose and DFHSP had the highest reactivity with larger pH reduce, higher browning index increase and higher antioxidant activity than other MRPs from other sugars. The antioxidant activities were increased with increasing temperatures and pressures of reaction. The highest antioxidant activity and sensory preference were obtained from MRPs with ribose at $140^{\circ}C$ with 2.8 kg/$cm^2$ for 30 mins.

Effect of Temperature Gradient on the Characteristics of GaN Nanorods Grown on R-plane Sapphire Substrates (기판 주변 반응 기체와 기판 사이의 온도 차이에 따른 r-면 사파이어 기판에 성장된 길화갈륨 나노 막대의 특성 변화 연구)

  • Shin, Bo-A;Kim, Chin-Kyo
    • Journal of the Korean Vacuum Society
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    • v.18 no.1
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    • pp.44-48
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    • 2009
  • The effect of temperature gradient between the substrate and ambient gas on the structural characteristics of GaN nanorods grown on r-plane sapphire substrates by hydride vapor phase epitaxy was investigated. The density, diameter, and length strongly depended on the tempearture gradient. In addition, the cross-sectional shape of the nanorrods at the end of growth was found to be more dependedent on the temperature of a substrate itself than the temperature gradient.

Optimization of the Reaction Conditions for (R)-Phenyl-1,2-ethanediol Preparation by Recombinant Epoxide Hydrolase from Caulobacter crescentus (재조합 Caulobacter crescentus 에폭사이드 가수분해효소를 이용한 광학활성 Diol 제조 조건의 최적화)

  • Lee, Ok-Kyung;Kim, Hee-Sook
    • Microbiology and Biotechnology Letters
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    • v.35 no.4
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    • pp.285-291
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    • 2007
  • Enantioconvergent hydrolysis process for the preparation of chiral diol from racemic epoxides by using the recombinant Caulobacter crescentus epoxide hydrolase (CcEH) in Escherichia coli BL21 (DE3) was optimized. For the optimization, the effects of detergent, temperature and product inhibition on the enantiopurity and the yield of diol were investigated. (R)-phenyl-1,2-ethanediol with 92% enantiomeric excess and 56% yield from 20 mM racemic styrene oxide was obtained by using the recombinant CcEH at the optimal condition of $10^{\circ}C$ and the addition of 2% (w/v) Tween 80. At 50 mM racemic styrene oxide was used as a substrate, (R)-phenyl-1,2-ethanediol was obtained with 87% enantiomeric excess and 77% yield. Racemic phenyl-1,2-ethanediol, (R)-phenyl-1,2-ethanediol and (S)-phenyl-1,2-ethanediol dramatically inhibited the hydrolytic activity of the recombinant CcEH. These results suggested that another EH with the regioselectivity on ${\beta}$-position of (R)-enantiomer and without feedback inhibition by products would be needed as the partner EH of C. crescentus EH.

Refining of Vacuum Residues by Aquathermolysis Reaction (Aquathermolysis 반응에 의한 감압잔사유의 개질)

  • Ko, Jin Young;Park, Dong Ho;Park, Seung-Kyu
    • Applied Chemistry for Engineering
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    • v.28 no.4
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    • pp.467-472
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    • 2017
  • In this study, the reforming reaction of vacuum residue (VR) was carried out using aquathermolysis reaction. VR showed a prone to decrease the amount of resins and asphaltenes in the constituents, and to increase saturates and aromatics when reacting with steam at 30 bar and above $300^{\circ}C$ for 24 h. This tendency became more evident when the amount of steam used was excessive than the amount of VR. When the aquathermolysis reaction was performed at $300^{\circ}C$ and 30 bar for 48 h, the VR composition was changed from the initial state (S/A/R/A = 7.3%/43.7%/25.6%/23.5%) to final state (S/A/R/A = 6.8%/57%/12.2%/24.0%), and the contents of the resins decreased by 13% and the aromatic compounds increased by 13%. The viscosity decreased from 880,000 cp to 290,000 cp by 68%. When 10% of decalin, which is easy to provide hydrogen, was added, the viscosity decreased by 68% in 24 h. The VR composition showed a reduction in the contents of resins and asphaltenes from 49% to 17% from the initial state (S/A/R/A = 7.3%/43.7%/25.6%/23.5%) to the final state (S/A/R/A = 4.5%/63.5%/12.5%/20.0%), and the content of aromatics was maximized to 63.5%. The gas layer formed by the aquathermolysis reaction in the reactor chamber was collected and analyzed by GC-MS spectroscopy. As a result, various hydrocarbon compounds such as ethylbenzene, octane and dimethylbenzene were detected.

Estimation of R-factor and Seismic Performance for RC IMRFs using N2 Method (N2 Method를 이용한 RC 중간모멘트 연성골조의 반응수정계수 및 내진성능 평가)

  • 윤정배;이철호;최정욱;송진규
    • Journal of the Earthquake Engineering Society of Korea
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    • v.6 no.6
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    • pp.33-39
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    • 2002
  • Response Modification Factor(R-factor) approach is currently implemented to reflect inelastic ductile behavior of the structures and to reduce elastic spectral demands from earthquakes to the design level. However R factors were set empirically and simply based on the professional committee consensus on observed performance of building structures during past earthquakes. Consequently some major shortcomings linked to the current R factor approach have been pointed out. Using reinforced concrete intermediate moment-resisting frames(RC IMRFs), an analytical procedure is presented in this paper to establish R factor rationally. To this end, analytical R values were evaluated based on N2 Method and compared with the values recommended by IBC 2000. Overall, the analytical results correlated well with the code values. However the results also revealed that R factor might strongly depend on the system fundamental period. As evidenced by the interstory drift index(IDI) analysis results of this study, current R-factor based(or, Life Safety based) design tends to fail in fulfilling other implicit and hopeful performance objectives such as immediate Occupancy and Collapse Prevention. Performance based design(PBD) appears to be a promising approach to meet the multi level seismic performance objectives assigned to the building structures of nowadays.

Homolytic Reactions of Isonitriles (이소니트릴의 자유라디칼반응)

  • Sung Soo Kim
    • Journal of the Korean Chemical Society
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    • v.24 no.3
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    • pp.250-258
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    • 1980
  • Various radicals may add to isonitriles to give imidoyl radcals RN=CR'. This may be also generated via abstraction of imidoyl hydrogen from imine in the following manner: RN=CR' + R"${\cdot}{\rightarrow}$ RN=CR' + R"-H Imidoyl radicals would be stabilized via two pathways, ${\beta}$-cleavage and atom transfer reactions. ${\beta}$-Cleavage may occur in two directions depending upon structure of the radicals. Cyanide transfer and the "so-called" normal ${\beta}$-cleavage are the two modes of ${\beta}$-cleavage. Addition of t-butoxy radical to t-butyl isocyanide 7 generates an imidoyl radical t-Bu-N=C-O-Bu-t, which undergoes ${\beta}$-cleavage to give t-butyl isocyanate and t-butyl radical. Addition of phenyl radical to 7 forms the intermediate radical t-Bu-N=$C-C_6H_5$, which decomposes to give benzonitrile and t-butyl radical. The t-butyl radical generated from the ${\beta}$-cleavage adds to 7 giving the radical t-Bu-N=C-Bu-t, which cleaves only to pivalonitrile and t-butyl radical, inducing radical chain isomerization. Trimethylsilyl radical adds to 7 to give the intermediate t-Bu-N=$C-Si(CH_3)_3$, which collapses to $(CH_3)_3$SiCN and a t-butyl radical.

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Kinetic Studies on Halogen Exchange of Substituted Benzenesulfonylbromides

  • Kim, Jaerok
    • Nuclear Engineering and Technology
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    • v.5 no.4
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    • pp.321-333
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    • 1973
  • The rates and activation parameters for the halide exchange reactions of substituted benzenesulfonylbromides (R-C$_{6}$H$_4$SO$_2$Br, R=p-MeO, p-$CH_3$, p-H, p-NO$_2$) in dry acetone at two temperatures were determined. It was found that the nucleophilicity order of Cl->I-$\geq$Br- for strong electron withdrawing-, and mild electron donating group, and of I-$\geq$Cl->Br- for strong electron donating group, Hammett plots showed slightly convoked characteristics which is similar to the plots of substituted benzenesulfonylchlorides, but contrary to the concaved nature for the halide exchange reactions of substituted benzyl chlorides. The rate of halogen exchange between benzenesulfonylbromide and lithium bromide decreased in the order of solvent : ($CH_3$)$_2$CO>$CH_3$CN》MeOH. The rates and activation parameters were also compared with those already known in the substituted benzenesulfonylchlorides. Theses were explained in terms of the structural properties of the transition state, and discussed the reaction mechanisms.s.

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