• Title/Summary/Keyword: Kinetics parameters

Search Result 610, Processing Time 0.029 seconds

Study of the Kinetics and Mechanisms of Alkoxy Radical Reactions in the Gas Phase (I). Arrhenius Parameters for t-Butoxy Radical Reactions with Isobutane and Cyclohexane

  • Song, Se-Ahn;Choo, Kwang-Yul
    • Bulletin of the Korean Chemical Society
    • /
    • v.5 no.1
    • /
    • pp.16-21
    • /
    • 1984
  • The relative Arrhenius parameters for t-butoxy radical decomposition (log $A_d$, $E_d$) and hydrogen abstraction of t-butoxy radical from hydrogen donor (log $A_d$, $E_d$) by competitive method were obtained as follows: for cyclohexane; log $A_a/A_d$ = -4.17 mole/l and $E_d-E_a$ = 9.01 kcal/mole, for isobutane; log $A_a/A_d$ = -5.70 mole/l and $E_e-E_a$= 11.0 kcal/mole. From the reported Arrhenius parameters for t-Butoxy radical decomposition reactions the parameters for t-Butoxy radical reactions with isobutane and cyclohexane are estimated to be log $A(l/mol{\cdot}sec)$ = 8.4, $E_a$ = 4.3 kcal/mol and $log A (l/mol{\cdot}sec)= 9.9,\;E_a$ = 6.3 kcal/mol, respectively.

Sensitivity study of parameters important to Molten Salt Reactor Safety

  • Sarah Elizabeth Creasman;Visura Pathirana;Ondrej Chvala
    • Nuclear Engineering and Technology
    • /
    • v.55 no.5
    • /
    • pp.1687-1707
    • /
    • 2023
  • This paper presents a molten salt reactor (MSR) design parameter sensitivity study using a nodal dynamic modelling methodology with explicitly modified point kinetics equation and Mann's model for heat transfer. Six parameters that can impact MSR safety are evaluated. A MATLAB-Simulink model inspired by Thorcon's 550MWth MSR is used for parameter evaluations. A safety envelope was formed to encapsulate power, maximum and minimum temperature, and temperature-induced reactivity feedback. The parameters are perturbed by ±30%. The parameters were then ranked by their subsequent impact on the considered safety envelope, which ranks acceptable parameter uncertainty. The model is openly available on GitHub.

Influence of the cathode catalyst layer thickness on the behaviour of an air breathing PEM fuel cell

  • Ferreira-Aparicio, Paloma;Chaparro, Antonio M.
    • Advances in Energy Research
    • /
    • v.2 no.2
    • /
    • pp.73-84
    • /
    • 2014
  • Fuel cells of proton exchange membrane type (PEMFC) working with hydrogen in the anode and ambient air in the cathode ('air breathing') have been prepared and characterized. The cells have been studied with variable thickness of the cathode catalyst layer ($L_{CL}$), maintaining constant the platinum and ionomer loads. Polarization curves and electrochemical active area measurements have been carried out. The polarization curves are analyzed in terms of a model for a flooded passive air breathing cathode. The analysis shows that $L_{CL}$ affects to electrochemical kinetics and mass transport processes inside the electrode, as reflected by two parameters of the polarization curves: the Tafel slope and the internal resistance. The observed decrease in Tafel slope with decreasing $L_{CL}$ shows improvements in the oxygen reduction kinetics which we attribute to changes in the catalyst layer structure. A decrease in the internal resistance with $L_{CL}$ is attributed to lower protonic resistance of thinner catalyst layers, although the observed decrease is lower than expected probably because the electronic conduction starts to be hindered by more hydrophilic character and thicker ionomer film.

Role of Diffusion in the Kinetics of Reversible Enzyme-catalyzed Reactions

  • Szabo, Attila;Zhou, Huan-Xiang
    • Bulletin of the Korean Chemical Society
    • /
    • v.33 no.3
    • /
    • pp.925-928
    • /
    • 2012
  • The accurate expression for the steady-state velocity of an irreversible enzyme-catalyzed reaction obtained by Shin and co-workers (J. Chem. Phys. 2001, 115, 1455) is generalized to allow for the rebinding of the product. The amplitude of the power-law ($t^{-1/2}$) relaxation of the free- and bound-enzyme concentrations to steady-state values is expressed in terms of the steady-state velocity and the intrinsic (chemical) rate constants. This result is conjectured to be exact, even though our expression for the steady-state velocity in terms of microscopic parameters is only approximate.

Curing Kinetics of the No-Flow Underfill Encapsulant

  • Jung, Hye-Wook;Han, Sang-Gyun;Kim, Min-Young;Kim, Won-Ho
    • Proceedings of the International Microelectronics And Packaging Society Conference
    • /
    • 2001.11a
    • /
    • pp.134-137
    • /
    • 2001
  • The cure kinetics of a cycloalipatic epoxy / anhydride / Co(II) system for a no-flow underfill encapsulant, has been studied by using a differential scanning calorimetry(DSC) under isothermal and dynamic conditions over the temperature range of $160^{\circ}C ~220^{\circ}C$. The kinetic analysis was carried out by fitting dynamic/isothermal heating experimental data to the kinetic expressions to determine the reaction parameters, such as order of reaction and reaction constants. Diffusion-controlled reaction has been observed as the cure conversion increases and successfully analyzed by incorporating the diffusion control term into the rate equation. The prediction of reaction rates by the model equation corresponded well to experimental data at all temperature.

  • PDF

The Effect of Pressure on the Rate of Solvolysis (Ⅲ) Kinetics on the Nucleophilic Substitution Reactions of Acyl- and Alkyl groups in Binary Solvents (가용매분해반응속도에 대한 압력의 영향(Ⅲ) 이성분용매내 Acyl류와 Alkyl류의 친핵성 치환반응의 속도론적 연구)

  • Kyong, Jin Burm;Park, Byoung Chun;Kwun, Oh Cheun
    • Journal of the Korean Chemical Society
    • /
    • v.41 no.9
    • /
    • pp.443-448
    • /
    • 1997
  • Kinetics for the solvolyses of acyl chlorides and alkyl chlorides in hydroxylic solvent mixtures have been measured by conductometric method at various temperatures and pressures. The activation parameters (${\Delta}V^{\neq},\; {\Delta}H^{\neq},\; {\Delta}S^{\neq}$) were estimated from the rate constants. The reactivities of these reactions were also estimated from the correlation of the activation volumes with the activation entropies.

  • PDF

Kinetics and Mechanism of Mutant O-acetylserine Sulfhydrylase-A (C43S) from Salmonella typhimurium LT-2

  • Yoon, Moon-Young
    • BMB Reports
    • /
    • v.29 no.3
    • /
    • pp.210-214
    • /
    • 1996
  • The pH dependence of the kinetic parameters of mutant O-acetylserine sulfhydrylase (OASS) from Salmonella typhimurium LT-2 has been determined in order to obtain information on the chemical mechanism. The initial velocity pattern obtained by varying the concentrations of OAS at several fixed concentrations of TNB, shows an intersection on the left of the ordinate at pH 7.0, indicating that the kinetic mechanism is a sequential mechanism in which substrate inhibition by OAS is observed while the wild type enzyme showed a ping pong mechanism. The values of $V/E_t$, $V/K_{OAS}E_{t}$ and $V/K_{TNB}E_{t}$ decreased by about 68%, 14% and 16% as compared with the wild type enzyme. The $V/K_{OAS}E_{t}$ is a pK of 6.5 on the acid side of the pH profile, and the $V/K_{TNB}$ is pH independent. As compared with the wild type enzyme, the pKs in the V/K profiles are shifted, reflecting that binding of the cofactor in free E:OAS is less asymmetric.

  • PDF

$CH_4$ Gas Sensor Utilizing Pd-SiC Schottky Diode (Pd-SiC 쇼트키 다이오드를 이용한 $CH_4$ 가스센서)

  • 김창교;이주헌;이영환
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
    • /
    • 1998.11a
    • /
    • pp.163-166
    • /
    • 1998
  • The mechanism of methane sensing by Pd-SiC diode was investigated over the temperature range of 400~$600^{\circ}C$. The effects or methane gas reaction on the parameters such as barrier height, initial rate of methane gas reaction are investigated. The methane gas reaction kinetics on the device are also discussed. The physical and chemical mechanism responsible for methane detection are proposed. Analysis of steady-state reaction kinetics using I-V method confirmed that methane gas reaction processes are responsible for the barrier height change in the diode.

  • PDF

The Crystallization Kinetics of CaO-MgO-Al2O3-SiO2 Glass System Using Thermal Analysis (열분석을 이용한 CaO-MgO-Al$_2$O$_3$-SiO$_2$의 결정화 기구의 연구)

  • 김형순
    • Journal of the Korean Ceramic Society
    • /
    • v.29 no.1
    • /
    • pp.9-14
    • /
    • 1992
  • Some of non-isothermal analysis methods are applied to CaO-MgO-Al2O3-SiO2 glass system to find the kinetics parameters of crystallisation, activation energy, Avrami component and frequency factor. The results using the non-isothermal analysis were compared to that of microstructure experiment. Analysis of the result has enabled to some methods to be to recommend as being the most appropriate equation to use in a glass system. It was shown that in the thermal analysis using the non-isothermal method of Kissinger, Augis-Bennett, Bansal, and Marotta, the calculation of activation energy is not much different, while Avrami component and frequency factor are different from applied each methods.

  • PDF

Adsorption Kinetic Study of Ruthenium Complex Dyes onto TiO2 Anodes for Dye-sensitized Solar Cells (DSSCs) (염료감응 태양전지용 루테늄 금속착체 염료의 이산화티타늄 전극에 대한 동적 흡착 연구)

  • An, Byeong-Kwan
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
    • /
    • v.24 no.11
    • /
    • pp.929-934
    • /
    • 2011
  • The adsorption kinetic study of ruthenium complex, N3, onto nanoporous titanium dioxide ($TiO_2$) photoanodes has been carried out by measuring dye uptake in-situ. Three simplified kinetic models including a pseudo first-order equation, pseudo second-order equation and intraparticle diffusion equation were chosen to follow the adsorption process. Kinetic parameters, rate constant, equilibrium adsorption capacities and related coefficient coefficients for each kinetic model were calculated and discussed. It was shown that the adsorption kinetics of N3 dye molecules onto porous $TiO_2$ obeys pseudo second-order kinetics with chemisorption being the rate determining step. Additionally the heterogeneous surface and the pore size distribution of porous $TiO_2$ adsorbents were also discussed.