• Title/Summary/Keyword: Reaction Mechanism

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The Trends in Methanol Oxidation Reaction Mechanisms and Electrochemical Oxidation Catalysts (메탄올 산화 반응 메커니즘과 전기화학 산화 촉매 최신 동향)

  • Sungyool Bong
    • Applied Chemistry for Engineering
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    • v.35 no.2
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    • pp.79-84
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    • 2024
  • Methane is an abundant and renewable hydrocarbon, but it causes global warming as a greenhouse gas. Therefore, methods to convert methane into useful chemicals or energy sources are needed. Methanol is a simple and abundant chemical that can be synthesized by the partial oxidation of methane. Methanol can be used as a chemical feedstock or a transportation fuel, as well as a fuel for low-temperature fuel cells. However, the electrochemical oxidation of methanol is a complex and multi-step reaction. To understand and optimize this reaction, new electrocatalysts and reaction mechanisms are required. This review discusses the methanol oxidation reaction mechanism, recent research trends, and future research directions.

Dynamic Modeling and Analysis of Flexible Mechanism With Joint Clearance (유연한 기구의 틈새관절 모델링 및 해석방법에 관한 연구)

  • 홍지수;김호룡
    • Transactions of the Korean Society of Mechanical Engineers
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    • v.18 no.12
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    • pp.3109-3117
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    • 1994
  • To operate a flexible mechanism in high speed its weight must be reduced as far as the structural strength does not decrease too much, but a light-weighted mechanism causes undesirable elastodynamic responses deteriorating the system performance. Besides, clearance within the connections of mechanisms causes rapid wear, increased noise and vibration. Even if the problems described above must be considered in the initial design stage, there has been no effective design process which takes account of the correlation between dynamic characteristics of flexible mechanism and the clearance effect at the joint. In this study, the generalized elastodynamic governing equations which include dynamic characteristics and boundary conditions of flexible mechanism are derived by variational calculus and solved by using FFM theory. To take the clearance effect at joint into account a new dynamic model is presented and also the method of modified stiffness/damping matrix is proposed to activate the dynamic clearance model, which cooperates with the developed governing equation very easily. As the results of this study, the proposed method(modified stiffness/damping matrix) to calculate clearance effect was proved to be superior to the existing one(force reaction method) in solution convergency and calculation performance. Besides this method can be easily adopted to the complex shape joint without calculation of reaction force direction.

Kinetics and Mechanism of Corrosion of ρ-alumina Bonded Alumina Castable by Molten Slag (ρ-알루미나결합 알루미나 캐스터블의 용융슬래그에 의한 침식기구)

  • 천승호;전병세
    • Journal of the Korean Ceramic Society
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    • v.40 no.10
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    • pp.1015-1020
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    • 2003
  • The Corrosion behavior of the matrix of the $\rho$-alumina bonded alumina vibrated castable was, on the basis of Jabsen's theory, elucidated by use of the Kingery's reaction mechanism. Corrosion of the matrix during induction period was controlled by the molecular diffusion. The temperature dependence of activation process is well established by the Arrhenius plots. The difference of Ca concentration between slag and interface is 23.2%, which causes a driving force of the materials transfer. The extent of the corrosion of the matrix is more deeper than that of the sintered mullite, but the corrosion mechanism can be well employed as the reaction mechanism proposed by the Kingery. The life time of the castable may be well estimated by the corrosion mechanism of Kingery.

The Study on the Mechanism for Oxidation Reaction of Boratabenzene by Cyclic Voltammetry (Cyclic Voltammetry를 이용한 Boratabenzene의 산화반응 Mechanism 연구)

  • Shin, Ueon-Sang
    • Analytical Science and Technology
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    • v.15 no.6
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    • pp.550-555
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    • 2002
  • The oxidation mechanism of boratabenzene was studied. As a model compound the ferrocene analogue (${\eta}^6$-1-Methylboratabenzene)(${\eta}^5$-Pentamethylcyclopentadiennyl)iron 3 was chosen. The complex underwent irreversible oxidation in the presence of ortho proton on the ring and a methyl group on the boron atom in methanol medium. Chemical oxidations with $Hg(OAc)_2$, $HgSO_4$, $Cu(OH)_2$, $AgCF_3SO_3$ or $FeCl_3$ in MeOH gave, via a transition state [3], at first the derivates 6 and 7, which were converted to each 8 and 9.

Kinetics of Reversible Consecutive Reactions

  • Park, Tae Jun
    • Bulletin of the Korean Chemical Society
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    • v.34 no.1
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    • pp.243-245
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    • 2013
  • Rate equations are exactly solved for the reversible consecutive reaction of the first-order and the time-dependence of concentrations is analytically determined for species in the reaction. With the assumption of pseudo first-order reaction, the calculation applies and determines the concentration of product accurately and explicitly as a function of time in the unimolecular decomposition of Lindemann and in the enzyme catalysis of Michaelis-Menten whose rate laws have been approximated in terms of reactant concentrations by the steady-state approximation.

Development of Voltammetric Urea Sensors Based Poly(3-methylthiophene) film (Poly(3-methylthiophene)막 위에 urease를 고착시킨 Voltammetric Urea Sensor의 개발)

  • 박성호;진준형;홍석인;민남기
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2000.11a
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    • pp.314-316
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    • 2000
  • Urea is detected as an indicator of renal disease in the human body. For these reasons, many biosensors for urea have been developed based on the enzymatic reaction of urea hydrolysis catalyzed by urease. Potentiometric method is applied reversible reaction system. But urea hydrolysis reaction may not has a reversible reaction mechanism in electrode surface. Therefore we applied to voltammtricmethod to obtain a sensitivity curve. The sensitivity of sensors was 34 ${\mu}$A/decade.

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Aminolysis of 2,4-Dinitrophenyl and 3,4-Dinitrophenyl 2-Thiophenecarboxylates: Effect of ortho-Nitro Group on Reactivity and Mechanism

  • Seo, Jin-A;Chun, Sun-Mee;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.29 no.8
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    • pp.1459-1463
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    • 2008
  • Second-order rate constants (kN) have been measured spectrophotometrically for reactions of 3,4-dinitrophenyl 2-thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % dimethyl sulfoxide at 25.0 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature for the aminolysis of 2. The curved Brønsted-type plot is similar to that reported for the corresponding reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (1). The reactions of 1 and 2 have been suggested to proceed through the same mechanism, i.e., through a zwitterionic tetrahedral intermediate ($T^{\pm}$) with a change in the rate-determining step. Substrate 2 is less reactive than 1 toward weakly basic amines (e.g., $pK_a$ < 10.4) but becomes more reactive as the basicity of amines increases further. Dissection of kN into the microscopic rate constants has revealed that the reaction of 2 results in a smaller $k_2/k_{-1}$ ratio but larger $k_1$ than the corresponding reaction of 1. Steric hindrance exerted by the ortho-nitro group has been suggested to be responsible for the smaller $k_1$ value found for the reactions of 1.

The Role of Lattice Oxygen in the Selective Catalytic Reduction of NOx on V2O5/TiO2 Catalysts (V2O5/TiO2 촉매의 선택적 환원촉매반응에서 격자산소의 역할)

  • Ha, Heon-Phil;Choi, Hee-Lack
    • Korean Journal of Materials Research
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    • v.16 no.5
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    • pp.323-328
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    • 2006
  • In situ electrical conductivity measurements on $V_2O_5WO_3/TiO_2$ catalysts were carried out at between 100 and $300^{\circ}C$ under pure oxygen, NO and $NH_3$ to investigate the reaction mechanism for ammonia SCR (selective catalytic reduction) de NOX. The electrical conductivity of catalysts changed irregularly with supply of NO. It was, however, found that the electrical conductivity change with ammonia supply was regular and the increase of electrical conductivity was mainly caused by reduction of the labile surface oxygen. The electrical conductivity change of catalysts showed close relationship with the conversion rate of NOx. Variation of conversion rate in atmosphere without gaseous oxygen also showed that labile lattice oxygen is indispensable in the initial stage of the de NOx reaction. These results suggest that liable lattice oxygen acts decisive role in the de NOx mechanism. They also support that de NOx reaction occurs through the Eley?Rideal type mechanism. The amount of labile oxygen can be estimated from the measurement of electrical conductivity change for catalysts with ammonia supply. This suggests that measurement of the change can be used as a measure of the de NOx performance.

Growth of Nano- and Microstructured Indium Nitride Crystals by the Reaction of Indium Oxide with Ammonia

  • Jung, Woo-Sik;Ra, Choon-Sup;Min, Bong-Ki
    • Bulletin of the Korean Chemical Society
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    • v.26 no.9
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    • pp.1354-1358
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    • 2005
  • Nano- and microstructured indium nitride crystals were synthesized by the reaction of indium oxide ($In_2O_3$) powder and its pellet with ammonia in the temperature range 580-700 ${^{\circ}C}$. The degree of nitridation of $In_2O_3$ to InN was very sensitive to the nitridation temperature. The formation of zero- to three-dimensional structured InN crystals demonstrated that $In_2O_3$ is nitridated to InN via two dominant parallel routes (solid ($In_2O_3$)-to-solid (InN) and gas ($In_2O$)-to-solid (InN)). The growth of InN crystals with such various morphologies was explained by the vapor-solid (VS) mechanism where the degree of supersaturation of In vapor determines the growth morphology and the vapor was mainly by the reaction of $In_2O$ with ammonia and partially by sublimation of solid InN. The pellet method was proven to be useful to obtain homogeneous InN nanowires.

Theoretical Study of the Reaction Mechanism for SiF2 Radical with HNCO

  • Hou, Li-Jie;Wu, Bo-Wan;Kong, Chao;Han, Yan-Xia;Chen, Dong-Ping;Gao, Li-Guo
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3738-3742
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    • 2013
  • The reaction mechanism of $SiF_2$ radical with HNCO has been investigated by the B3LYP method of density functional theory(DFT), while the geometries and harmonic vibration frequencies of reactants, intermediates, transition states and products have been calculated at the B3LYP/$6-311++G^{**}$ level. To obtain more precise energy result, stationary point energies were calculated at the CCSD(T)/$6-311++G^{**}$//B3LYP/$6-311++G^{**}$ level. $SiF_2+HNCO{\rightarrow}IM3{\rightarrow}TS5{\rightarrow}IM4{\rightarrow}TS6{\rightarrow}OSiF_2CNH(P3)$ was the main channel with low potential energy, $OSiF_2CNH$ was the main product. The analyses for the combining interaction between $SiF_2$ radical and HNCO with the atom-in-molecules theory (AIM) have been performed.