• Bulletin of the Korean Chemical Society
• /
• v.32 no.spc8
• /
• pp.2973-2977
• /
• 2011

It has been known that the inertial dynamics has a little effect on the reaction rate in solutions. In this work, however, we find that for diffusion-controlled reactions between a ligand and a receptor on the cell surface there is a noticeable inertial dynamic effect on the reaction rate. We estimate the magnitude of the inertial dynamic effect by comparing the approximate analytic results obtained with and without the inertial dynamic effect included. The magnitude of the inertial dynamic effect depends on the friction coefficient of the ligand as well as on the relative scale of the receptor size to the distance traveled by the ligand during its velocity relaxation time.

• Bulletin of the Korean Chemical Society
• /
• v.27 no.8
• /
• pp.1181-1185
• /
• 2006

By using two different computer simulation methods, of which one produces exact results while the other is based on the Wilemski-Fixman closure approximation, we evaluate the utility of closure approximation in calculating the rates of diffusion-controlled reactions involving a reactant with multiple reaction sites. We find that errors in the estimates of steady-state rate constants due to closure approximation are not so large. We thus propose an approximate analytic expression for the rate constant based on the closure approximation.

• Transactions of the Korean Society of Mechanical Engineers B
• /
• v.21 no.9
• /
• pp.1174-1184
• /
• 1997

Extinction characteristics of pure hydrogen-oxygen diffusion flames, at high pressures in the neighborhood of the critical pressure of oxygen, is numerically studied by employing counterflow diffusion flame as a model flame let in turbulent flames in rocket engines. The numerical results show that extinction strain rate increases almost linearly with pressure up to 100 atm, which can be explained by comparison of the chain-branching-reaction rate with the recombination-reaction rate. Since contributions of the chain-branching reactions, two-body reactions, are found to be much greater than those of the recombination reactions, three-body reactions, extinction is controlled by two-body reactions, thereby resulting in the linearity of extinction strain rate to pressure. Therefore, it is found that the chemical kinetic behaviors don't change up to 100 atm. Consideration of the pressure fall-off reactions shows a slight increase in extinction strain rate, but does not modify its linearity to pressure. The reduced kinetic mechanisms, which were verified at low pressures, are found to be still valid at high pressures and show good qualitative agreement in prediction of extinction strain rates. Effect of real gas is negligible on chemical kinetic behaviors of the flames.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.3
• /
• pp.862-868
• /
• 2012

Based on the recently derived general expression for the rates of diffusion-controlled reactions, we calculate the rates of dismutation of the superoxide anion radical catalyzed by Cu/Zn superoxide dismutases (SOD). This is the first attempt to calculate the absolute rates of diffusion-controlled enzyme reactions based on the atomiclevel molecular dynamics simulations. All solvent molecules are included explicitly and the effects of the structural flexibility of enzyme, especially those of side chain motions near the active site, are included in the present calculation. In addition, the actual mobility of the substrate molecule is taken into account, which may change as the molecule approaches the active site of enzyme from the bulk solution. The absolute value of the rate constant for the wild type SOD reaction obtained from MD simulation is shown to be in good agreement with the experimental value. The calculated reactivity of a mutant SOD is also in agreement with the experimental result.

• Journal of Powder Materials
• /
• v.4 no.3
• /
• pp.196-204
• /
• 1997

Joining of AIN ceramics to W and Cu by active-metal brazing method was tried with use of (Ag-Cu)-Ti alloy as insert-metal. Joints were produced under various conditions of temperature, holding time and Ti-content in (Ag-Cu) alloy Reaction and microstructural development in bonded interface were investigated through observation and analysis by SEM/EDS, EPMA and XRD. Joint strengths were measured by shear test. Bonded interface consists of two layers: an insert-metal layer of eutectic Ag- and Cu-rich phases and a reaction layer of TiN. Thickness of reaction layer increases with bonding temperature, holding time and Ti-content of insert-metal. It was confirmed that the growth of reaction layer is a diffusion-controlled process. Activation energy for this process was 260 KJ/mol which is lower than that for N diffusion in TiN. Maximum shear strength of 108 MPa and 72 MPa were obtained for AIN/W and AIN/Cu joints, respectively. Relationship between processing variables, joint strength and thickness of reaction layer was also explained.

• Macromolecular Research
• /
• v.10 no.5
• /
• pp.259-265
• /
• 2002

The cure kinetics of blends of epoxy (DGEBA, diglycidyl ether of bisphenol A)/anhydride resin with polyamide copolymer, poly(dimmer acid-co-alkyl polyamine), were studied using differential scanning calorimetry (DSC) under isothermal condition. On increasing the amount of polyamide copolymer in the blends, the reaction rate was increased and the final cure conversion was decreased. Lower values of final cure conversions in the epoxy/(polyamide copolymer) blends indicate that polyamide hinders the cure reaction between the epoxy and the curing agent. The value of the reaction order, m, for the initial autocatalytic reaction was not affected by blending polyamide copolymer with epoxy resin, and the value was approximately 1.3, whereas the reaction order, n, for the general n-th order of reaction was increased by increasing the amount of polyamide copolymer in the blends, and the value increased from 1.6 to 4.0. A diffusion-controlled reaction was observed as the cure conversion increased and the rate equation was successfully analyzed by incorporating the diffusion control term for the epoxy/anhydride/(polyamide copolymer) blends. Complete miscibility was observed in the uncured blends of epoxy/(polyamide copolymer) up to 120 $^{\circ}C$, but phase separations occurred in the early stages of the curing process at higher temperatures than 120 "C. During the curing process, the cure reaction involving the functional group in polyamide copolymer was detected on a DSC thermogram.gram.

• Journal of the Korean Ceramic Society
• /
• v.38 no.10
• /
• pp.881-885
• /
• 2001

Kinetics and mechanisms of intermediate phases formation in $Ba(Mg_{1/3}Ta_{2/3})O_3$, obtained by a solid state reaction were studied. $Ba{Ta_2}{O_6}$ and ${Ba_4}{Ta_2}{O_9}$ as intermediate products were first formed at $700^{\circ}C$. $Ba(Mg_{1/3}Ta_{2/3})O_3$ was appeared at $800^{\circ}C$. Several reactions take place on heating process. $Ba{Ta_2}{O_6}$ is found at the first stage of the reaction, and then $Ba{Ta_2}{O_6}$ or ${Ba_4}{Ta_2}{O_9}$ react with MgO to form $Ba(Mg_{1/3}Ta_{2/3})O_3$. The reaction of $Ba(Mg_{1/3}Ta_{2/3})O_3$ formation does not complete until fired at $1350^{\circ}C$ for 60 min. The kinetics of solid-state reaction between powdered reactants was controlled by diffusion mechanism, and can be explained by the Jander's model for three-dimensional diffusion.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.8 no.1
• /
• pp.1-7
• /
• 2010

In the present work, an electrowinning process in the LiCl-KCl/Cd system is considered to model and analyze the electrotransport of the actinide and rare-earth elements. A simple dynamic modeling of this process was performed by taking into account the material balances and diffusion-controlled electrochemical reactions in a diffusion boundary layer at an electrode interface between the molten salt electrolyte and liquid cadmium cathode. The proposed modeling approach was based on the half-cell reduction reactions of metal chloride occurring on the cathode. This model demonstrated a capability for the prediction of the concentration behaviors, a faradic current of each element and an electrochemical potential as function of the time up to the corresponding electrotransport satisfying a given applied current based on a galvanostatic electrolysis. The results of selected case studies including five elements (U, Pu, Am, La, Nd) system are shown, and a preliminary simulation is carried out to show how the model can be used to understand the electrochemical characteristics and provide better information for developing an advanced electrowinner.

• Proceedings of the KWS Conference
• /
• 2002.10a
• /
• pp.475-480
• /
• 2002

The reliability of the solder joint is affected by type and extent of the interfacial reaction between solder and substrates. Therefore, understanding of intermetallic compounds produced by soldering in electronic packaging is essential. In-based alloys have been favored bonding devices that demand low soldering temperatures. For photonic and fiber optics packaging, m-based solders have become increasingly attractive as a soldering material candidate due to its ductility. In the present work, the interfacial reactions between indium solder and bare Cu Substrate are investigated. For the identification of intermetallic compounds, both Scanning Electron Microscopy(SEM) and X-Ray Diffraction(XRD) were employed. Experimental results showed that the intermetallic compounds, such as Cu$_{11}$In$_{9}$ was observed for bare Cu substrate. Additionally, the growth rate of these intermetallic compounds was increased with the reaction temperature and time. We found that the growth of the intermetallic compound follows the parabolic law, which indicates that the growth is diffusion-controlled.d.

• Elastomers and Composites
• /
• v.50 no.2
• /
• pp.92-97
• /
• 2015

A study on reaction kinetics for a PTMG/TDI prepolymer with 2,2'-dichloro-4,4'-methylenedianiline (MOCA), of which formulations may be generally used for fabricating high performance polyurethane elastomers, was peformed using non-isothermal differential scanning calorimetry (DSC). A number of thermograms were obtained at several constant heating rates, and analysed using Flynn-Wall-Ozawa (FWO) isoconversional method for activation energy, $E_a$ and extended-Avrami equation for reaction order, n. Urea formation reaction of the present system was observed to occur through the simple exothermic reaction process in the temperature range of $100{\sim}130^{\circ}C$ for the heating rate of $3{\sim}7^{\circ}C/min$. and could be well-fitted with generalized sigmoid function. Though activation energy was nearly constant as $53.0{\pm}0.5kJ/mol$, it tended to increase a little at initial stage, but it decreases at later stage by the transformation into diffusion-controlled reaction due to the increased viscosity. Reaction order was evaluated as about 2.8, which was somewhat higher than the generally well-known $2^{nd}$ order values for the various urea reactions. Both the reaction order and reaction rate explicitly increased with temperature, which was considered as the indication of occurring the side reactions such as allophanate or biuret formation.