• 제목/요약/키워드: Reaction rates

검색결과 1,362건 처리시간 0.031초

치환 2-Phenylethyl arenesulfonate 류와 치환 피리딘류의 Menschutkin 형 반응에 관한 치환기 효과 (Substituent Effects for the Menschutkin-Type Reaction of Substituted 2-Phenylethyl arenesulfonates with Substituted Pyridines)

  • 여수동;김중협
    • 대한화학회지
    • /
    • 제33권4호
    • /
    • pp.413-418
    • /
    • 1989
  • 치환 2-phenylethyl tosylate와 치환 피리딘을 아세토니트릴에서, 2-phenylethyl m-nitrobenzenesulfonate(2-PNS)와 치환 피리딘을 아세토니트릴과 메탄올 용매 중에서 각각 반응시켰다. 기질과 친핵체 다같이 전자를 미는 치환기는 반응속도를 증가시켰다. 이들 결과는 전이상태 변화를 예측하는 More O'Ferral과 양자역학적인 모델에서 결합 파괴가 결합형성보다 더 진전된 $S_N2$ 메카니즘으로 진행함을 보였다. 전이상태 변화는 양자 역학적인 모델의 예측이 실험치와 잘 일치하였고 이탈기에서는 More O'Ferral 도시가 잘 맞지 않았다. 2-PNS 와 피리딘류와의 반응에서는 아세토니트릴이 메탄올용매보다 반응이 빨랐다.

  • PDF

Fabrication of β-SiAlONs by a Reaction-Bonding Process Followed by Post-Sintering

  • Park, Young-Jo;Noh, Eun-Ah;Ko, Jae-Woong;Kim, Hai-Doo
    • 한국세라믹학회지
    • /
    • 제46권5호
    • /
    • pp.452-455
    • /
    • 2009
  • A cost-effective route to synthesize $\beta$-SiAlONs from Si mixtures by reaction bonding followed by post-sintering was investigated. Three different z values, 0.45, 0.92 and 1.87, in $Si_{6-z}Al_zO_zN_{8-z}$ without excess liquid phase were selected to elucidate the mechanism of SiAlON formation and densification. For RBSN (reaction-bonded silicon nitride) specimens prior to post-sintering, nitridation rates of more than 90% were achieved by multistep heating to $1400^{\circ}C$ in flowing 5%$H_2$/95%$N_2$; residual Si was not detected by XRD analysis. An increase in density was acquired with increasing z values in post-sintered specimens, and this tendency was explained by the presence of higher amounts of transient liquid phase at larger z values. Measured z values from the synthesized $\beta$-SiAlONs were similar to the values calculated for the starting compositions. Slight deviations in z values between measurements and calculations were rationalized by a reasonable application of the characteristics of the nitriding and post-sintering processes.

유동층 반응기에서 카본블랙 촉매를 이용한 프로판의 촉매 분해에 의한 수소생산 연구 (Hydrogen production by catalytic decomposition of propane over carbon black catalyst in a fluidized bed)

  • 정재욱;남우석;윤기준;이동현;한귀영
    • 한국신재생에너지학회:학술대회논문집
    • /
    • 한국신재생에너지학회 2006년도 춘계학술대회
    • /
    • pp.85-88
    • /
    • 2006
  • A fluidized bed reactor made of quartz with 0.055m I.D. and 1.0m in height was employed for the thermocatalytic decomposition of propane to produce $CO_2$-free hydrogen. The fluidized bed was proposed for the continuous withdraw of product carbons from the reactor. The propane decomposition rate used carbon black N33O as a catalyst. The propane decomposition reaction was carried out at the temperature range of $600{\sim}800^{\circ}C$, paropane gas velocity of $1.0 U_{mf}\;3.0U_{mf}$ and the operating pressure of 1.0 atm. Effect of operating parameters such as reaction temperature, gas velocity on the reaction rates was investigated. The carbon which was by-product of methane decomposition reaction was deposited on the catalyst surface that was observed by SEM. Resulting production in our experiment were not only hydrogen but also several by products such as methane, ethylene, ethane, and propylene.

  • PDF

수모델을 사용한 RH 진공 탈가스장치에서의 추가 버블링 효과 (Effects of Additional Bubbling on RH Vacuum Degassing Process with Water Model Experiment)

  • 장영환;김영태;이경우
    • 대한금속재료학회지
    • /
    • 제48권5호
    • /
    • pp.424-429
    • /
    • 2010
  • In the RH process, it is possible to obtain quicker processing times by enhancing the decarburization rates at a low carbon range of steel melt through Ar gas injection into the vacuum vessel. The RH decarburization reaction was simulated through a dissolved oxygen removal reaction by injecting nitrogen into a 1/8 scale RH water model system. The gas nozzles for the N$_{2}$ injection into the vacuum vessel were located at the lowest level of the vessel's outer wall. The nitrogen bubbling in the vacuum vessel resulted in an increase in the reaction rate constant, which rose in accordance with an increase in the bubbling flow rate and number of nozzles used. However, there was almost no variation in the reaction rate constant, which depended on the horizontal positions of the bubbling nozzles.

연소합성법을 이용한 방사성폐기물 고화체 Hollandite 분말 합성 (Synthesis of Hollandite Powders as a Nuclear Waste Ceramic Forms by a Solution Combustion Synthesis)

  • 정충환;정수지
    • 한국재료학회지
    • /
    • 제33권10호
    • /
    • pp.385-392
    • /
    • 2023
  • A solution combustion process for the synthesis of hollandite (BaAl2Ti6O16) powders is described. SYNROC (synthetic rock) consists of four main titanate phases: perovskite, zirconolite, hollandite and rutile. Hollandite is one of the crystalline host matrices used for the disposal of high-level radioactive wastes because it immobilizes Sr and Lns elements by forming solid solutions. The solution combustion synthesis, which is a self-sustaining oxi-reduction reaction between a nitrate and organic fuel, generates an exothermic reaction and that heat converts the precursors into their corresponding oxide products in air. The process has high energy efficiency, fast heating rates, short reaction times, and high compositional homogeneity. To confirm the combustion synthesis reaction, FT-IR analysis was conducted using glycine with a carboxyl group and an amine as fuel to observe its bonding with metal element in the nitrate. TG-DTA, X-ray diffraction analysis, SEM and EDS were performed to confirm the formed phases and morphology. Powders with an uncontrolled shape were obtained through a general oxide-route process, confirming hollandite powders with micro-sized soft agglomerates consisting of nano-sized primary particles can be prepared using these methods.

N-Oxidation of Pyrazines by Bromamine-B in Perchloric Acid Medium: Kinetic and Mechanistic Approach

  • Puttaswamy;Shubha, J.P.
    • Bulletin of the Korean Chemical Society
    • /
    • 제30권9호
    • /
    • pp.1939-1945
    • /
    • 2009
  • Kinetic investigations on the oxidation of pyrazine and four 2-substituted pyrazines viz., 2-methylpyrazine, 2-ethylpyrazine, 2-methoxypyrazine and 2-aminopyrazine by bromamine-B (BAB) to the respective N-oxides have been studied in HCl$O_4$ medium at 303 K. The reactions show identical kinetics being first-order each in $[BAB]_o\;and\;[pyrazine]_o$, and a fractional- order dependence on $[H^+]$. Effect of ionic strength of the medium and addition of benzenesulfonamide or halide ions showed no significant effect on the reaction rate. The dielectric effect is positive. The solvent isotope effect was studied using $D_2$O. The reaction has been studied at different temperatures and activation parameters for the composite reaction have been evaluated from the Arrhenius plots. The reaction showed 1:1 stoichiometry and the oxidation products of pyrazines were characterized as their respective N-oxides. Under comparable experimental conditions, the oxidation rate of pyrazines increased in the order: 2-aminopyrazine > 2-methoxypyrazine > 2-ethylpyrazine > 2-methylpyrazine > pyrazine. The rates correlate with the Hammett $\sigma$ relationship and the reaction constant $\rho$ was found to be -0.8, indicating that electron donating centres enhance the rate of reaction. An isokinetic temperature of $\beta$ = 333 K, indicated that the reaction was enthalpy controlled. A mechanism consistent with the experimental results has been proposed in which the rate determining step is the formation of an intermediate complex between the substrate and the diprotonated species of the oxidant. The related rate law in consistent with observed results has been deduced.

S-Thiolation and Oxidation of Glycogen Phosphorylase b and Peroxidation of Liposome Initiated by Free Radical Species

  • Lee, Kyu-Sun;Lee, Hyung-Min;Park, Young-Mee;Chang, Byeong-Doo;Chung, Tae-Young;Choi, Eun-Mi
    • BMB Reports
    • /
    • 제29권1호
    • /
    • pp.81-87
    • /
    • 1996
  • The relationship of S-thiolation and oxidation of glycogen phosphorylase b and peroxidation of phosphatidyl choline liposome by xanthine oxidase (XOD), 2,2'-azobis(2-amidinopropane) hydrochloride (AAPH), and 2,2'-azobis(dimethylvaleronitrile) (AMVN)-generated free radicals was investigated, Glycogen phosphorylase b was S-thiolated in the presence of glutathione and oxidized in the absence of it by XOD, AAPH and AMVN. In XOD-initiated reaction, the rates of S-thiolation and oxidation of phosphorylase were very similar and addition of liposome to the reaction mixture showed little inhibition of the modifications. In AAPH-initiated reaction, the rate of oxidation was higher than that of S-thiolation and addition of liposome increased oxidation of the protein but had no effect on S-thiolation. In AMVN-initiated reaction, S-thiolation was higher than oxidation and addition of liposome increased S-thiolation remarkably but showed no effect on oxidation. The effect of liposome on modifications of protein in AAPH and AMVN reaction seemed to be caused by certain reactive degradation products or intermediates of liposome by free radical attack. Peroxidation of liposome was not observed in XOD-initiated reaction. Liposome was gradually peroxidized by AAPH reaction. The peroxidation was inhibited by addition of GSH and phosphorylase. Peroxidation of liposome by AMVN was extreamly fast, and was not affected by GSH and phosphorylase.

  • PDF

반응성 올리고머 및 메타아크릴레이트/SBS 블렌드의 광중합 (Photopolymerization of Reactive Oligomers and Methacrylate/SBS Blends)

  • 최영선;류봉기
    • 폴리머
    • /
    • 제27권5호
    • /
    • pp.421-428
    • /
    • 2003
  • 반응성 올리고머 및 메타아크릴레이트/SBS블렌드의 확산에 의해 제어되는 광중합 반응 특성을 ATR-FTR을 이용하여 고찰하였다. 광중합 속도는 반응 초기 단계에서는 자가 가속 현상을 보이며 반응 속도가 급격하게 증가하여 반응이 진행함에 따라 확산에 의한 반응 지연 현상이 관찰된다. 확산 제어항이 도입된 반응 기구 속도식으로 반응 속도를 해석한 결과 전체 반응 구간에서 실험 결과와 잘 일치하였다. SBS의 도입을 위해 사용된 반응성 용매인 N-비닐피롤리돈 (NVP)의 첨가에 의해서 최종 전환율에 이르는 시간은 거의 일정하였으나 전환율은 NVP의 높은 반응성으로 인하여 증가하는 경향을 보였다. 중합 반응 속도도 NVP 첨가에 의하여 증가하는 경향을 보였다. SBS의 첨가시 NVP-SBS의 함량이 10 phr까지는 동일한 전환율 거동을 보이나 NVP-SBS의 함량이 20 phr에서는 현저히 떨어지게 되는데 이는 NVP-SBS의 함량이 20 phr에서는 블렌드의 점도가 증가하여 반응에 영향을 주는 것으로 보인다. NVP-SBS의 함량이 증가함에 따라 중합 반응 속도는 점진적으로 감소함을 알 수 있었다. 메타아크릴레이트./SBS의 블렌드는 상온과 여러 높은 온도 범위에서 상분리가 관찰되지 않았으며 광중합 반응 후에도 투명한 준-IPN을 형성하여 성공적으로 필름 및 코팅에 적용할 수 있었다.

햄스터 H-Y항체와 중합효소연쇄반응을 이용한 소 수정란의 성감별 (Sex determination of bovine embryos with hamster H-Y antibody and by polymerase chain reaction)

  • 유일정;김용준;이경광
    • 대한수의학회지
    • /
    • 제39권1호
    • /
    • pp.189-203
    • /
    • 1999
  • To determine sex of bovine embryos using hamster histocompatibility Y(H-Y) antibodies, bovine compact morulae were incubated for 6 hours in TCM199 supplemented with 10% hamster H-Y antiserum and the embryos with developmental arrest were diagnosed as male embryos, while the embryos showing development during the incubation as female embryos. This presumptive embryo sexing was confirmed by polymerase chain reaction(PCR)method. 1. In the result of hamster sperm cytotoxicity test to measure H-Y antibody titer, the rate of dead sperm was considerably lower in H-Y antiserum absorbed with hamster male splenocytes than in H-Y antiserum absorbed with hamster female splenocytes or H-Y antiserum unabsorbed with splenocytes(p<0.01). 2. The rate of oocytes fertilized in vitro and the rate of blastocysts of the fertilized oocytes were 58.5% and 32.4%, respectively. The rate of blastocysts on day 8 was 15.9%, denoting the highest rate during whole culture period posterior to in vitro fertilization (IVF). 3. The bovine 16 cell and compact morulae embryos incubated in the medium supplemented with hamster H-Y antibodies showed 37.1% and 48.9% of developmental arrest which were diagnosed as male, respectively, and rates of redeveloped embryos from the arrested were 24.1% in 16 cell and 44.3% in compact morulae embryos, respectively, denoting higher rate of sex determination and rate of redevelopment in compact morulae than 16 cell embryos. 4. Bovine compact morulae of Korean cattle and Holstein were treated with hamster H-Y antibodies for sex determination and the rates of developmental arrest(diagnosed as male) were 48.4% for Korean cattle and 47.9% for Holstein, respectively. The rates of redeveloped embryos to blastocyst after treatment were 42.6% for Korean cattle and 41.8% for Holstein, respectively, showing no significant differences of sex determination and redevelopment between both breed. 5. The sex determination of bovine embryos(Korean cattle and Holstein) using hamster H-Y antibodies was diagnosed by PCR for confirmation, denoting the rates of 86.1% for Korean cattle and 85.9% for Holstein male embryos, respectively, and the rates of 91.9% for Korean cattle and 90.1% for Holstein female embryos, respectively, with no significant differences of sex determination between both breed. These results indicated that hamster H-Y antibodies can be usable for sex determination of bovine embryos of Korean cattle and Holstein, the viability of bovine embryos was sustained while being cultured in the medium supplemented with hamster H-Y antibodies of appropriate titer and sex determination of bovine embryos by PCR can be feasible for confirmation.

  • PDF

Ni-Al-$ZrH_2$ 연료극을 사용한 용융탄산염 연료전지의 온도의 영향 (Effect of operating temperature using Ni-Al-$ZrH_2$ anode in molten carbonate fuel cell)

  • 서동호;장성철;윤성필;남석우;오인환;임태훈;홍성안;한종희
    • 한국신재생에너지학회:학술대회논문집
    • /
    • 한국신재생에너지학회 2010년도 춘계학술대회 초록집
    • /
    • pp.134-134
    • /
    • 2010
  • Fuel cell is a device that directly converts chemical energy in the form of a fuel into electrical energy by way of an electrochemical reaction. In the anode for a high temperature fuel cell, nickel or nickel alloy has been used in consideration of the cost, oxidation catalystic ability of hydrogen which is used as fuel, electron conductivity, and high temperature stability in reducing atmosphere. Most MCFC stacks currently operate at an average temperature of $650^{\circ}C$. There is some gains with decreased temperature in MCFC to diminish the electrolyte loss from evaporation and the material corrosion, which could improve the MCFC life. However, operating temperature has a strong related on a number of electrode reaction rates and ohmic losses. Baker et al. reported the effect of temperature (575 to $650^{\circ}C$). The rates of cell voltage loss were 1.4mV/$^{\circ}C$ for a reduction in temperature from 650 to $600^{\circ}C$, and 2.16mV/$^{\circ}C$ for a decrease from 600 to $575^{\circ}C$. The two major contributors responsible for the change in cell voltage with reducing operation temperature are the ohmic polarization and electrode polarization. It appears that in the temperature range of 550 to $650^{\circ}C$, about 1/3 of the total change in cell voltage with decreasing temperature is due to an increase in ohmic polarization, and the electrode polarization at the anode and cathode. In addition, the oxidation reaction of hydrogen on an ordinary nickel alloy anode in MCFC is generally considered to take place in the three phase zone, but anyway the area contributing to this reaction is limited. Therefore, in order to maintain a high performance of the fuel cell, it is necessary to keep this reaction responsible area as wide as possible, that is, it is needed to keep the porosity and specific surface area of the anode at a high level. In this study effective anodes are prepared for low temperature MCFC capable of enhancing the cell performance by using zirconium hydride at least in part of anode material.

  • PDF