• Bulletin of the Korean Chemical Society
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• v.35 no.11
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• pp.3313-3318
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• 2014

The reaction mechanism of Lead ions catalyzing complexation reactions between TIPP and metal ions was investigated by researching the kinetics of the formation of metalloporphyrins by UV/Vis-spectra, and verified by exploring the formation of metalloporphyrins catalyzed by acetic acid. Kinetics studies suggested that the fluctuations of reaction rate indicated the formation of metalloporphyrin was step-wise, including the pre-equilibrium step (the coordination of the pyrrolenine nitrogens to $Mn^+$) and the rate-controlling step (the deprotonation of the pyrrole proton). In the pre-equalization step, a sitting-atop (SAT) structure formed first with the complexation between larger radius of $Pb^{2+}$ and TIPP, changed the activation, then $Pb^{2+}$ left with the smaller radius of metal ions attacking from the back of the porphyrin ring center. In the rate-controlling step, two pyrrole protons dissociated to restore a stable structure. This was verified by adding acetic acid at different reaction times.

• Korean Journal of Materials Research
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• v.26 no.7
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• pp.382-387
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• 2016

Gas hydrates are crystalline solids in which gas molecules (guests) are trapped in water cavities (hosts) that are composed of hydrogen-bonded water molecules. During the formation of gas hydrates in seawater, the equilibria and kinetics are then affected by salinity. In this study, the effects of salinity on the equilibria of $CO_2$ and R134-a gas hydrates has been investigated by tracing the changes of operating temperature and pressure. Increasing the salinity by 1.75% led to a drop in the equilibrium temperature of about $2^{\circ}C$ for $CO_2$ gas hydrate and $0.38^{\circ}C$ for R-134a gas hydrate at constant equilibrium pressure; in other words, there were rises in the equilibrium pressure of about 1 bar and 0.25 bar at constant equilibrium temperature, respectively. The kinetics of gas hydrate formation have also been investigated by time-resolved in-situ Raman spectroscopy; the results demonstrate that the increase of salinity delayed the formation of both $CO_2$ and R134-a gas hydrates. Therefore, various ions in seawater can play roles of inhibitors for gas hydrate formation in terms of both equilibrium and kinetics.

• Preventive Nutrition and Food Science
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• v.12 no.3
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• pp.131-134
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• 2007

The kinetic analyses for thermal products of alpha-, gamma- and delta-tocopherols during heating as functions of temperature and time were studied. Alpha-, gamma- and delta-tocopherols dissolved in glycerol were heated at $100{\sim}200^{\circ}C$ for $5{\sim}60$ min. The thermal products were separated by hexane extraction and analyzed by HPLC using a reversed phase ${\mu}-Bondapak$ $C_{18}-column$ with two kinds of elution solvents in a gradient mode. The formation kinetics of thermal products of tocopherols followed a first-order kinetic model. The formation rate of thermal products of tocopherols was dependent on heating temperatures and heating times. The activation energy and enthalpy for the thermal products of ${\gamma}-and$ ${\delta}-tocopherols$ were higher than those for ${\alpha}-tocopherol$ as in the case of the oxidative degradation kinetics of tocopherol. The magnitude order of the activation energy was ${\gamma}->{\delta}->{\alpha}-tocopherol$.

• Journal of the Korean Ceramic Society
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• v.16 no.2
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• pp.99-105
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• 1979

Themogravimetric analysis was used to investigate the kinetics of the $Si_3N_4$ formation from Korean rice hulls in the temperature range from $1990^{\circ}C$ to $1370^{\circ}C$. The experimental results indicated that the reaction rate controlling step in the overall process is the diffusion of CO gas from the surface of carbon particle to main body of $N_2$ gas fluid through the stagnant gas film around the carbon particle. The kinetics followed a nearly linear rate law at the initil reaction stage. The activiation energy for the formation of $Si_3N_4$ from Korean rice hulls was 43.5Kcal/mole.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.8 no.5
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• pp.1042-1046
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• 2007

In this study, we investigated the mechanism responsible for the thermal stability of CoSi by addition of a foreign chemical element. Addition of W was found to increase the heat of formation of CoSi. This increase was claimed to inhibit the glass formation, which is preferred by silicide formation kinetics depicted by the maximum system energy degradation rate. In this case, there forms at the interface between CoSi and Si wafer a crystalline structure, the effective diffusion coefficient of which is much less than the self-diffusion rate provided by the glass. It was stated that the phase transition requires a higher thermal energy as the consequence, thereby enhancing the thermal stability of CoSi.

• Cement
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• s.31
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• pp.29-35
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• 1969

• Journal of the Korean Chemical Society
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• v.16 no.2
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• pp.84-92
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• 1972

A mechanism for the ring formation of nickel phthalocyanine (Ni-Pc) has been proposed based on chemical kinetics. The effect of the catalyst on the rate was examined, and ammonium molybdate has been found to be the most effective. The reaction order of the ring formation was determined to be of the 1st order over all, with only the concentration of urea affecting the rate of the ring formation. All the results including thermodynamic parameters support a conclusion that the rate-determining step seems to be the enolization of the urea-catalyst transition complex, followed by fast decomposition of the tautomeric enolized urea into ammonia and isocyanic acid. These intermediates then reacted with the phthalic anhydride to form imino and diimino-phthalimide, which condense to form nickel phthalocyanine in the presence of the nickel cation.

• Journal of the Korean Chemical Society
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• v.9 no.3
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• pp.148-151
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• 1965

Kinetics of reactions of chloride and bromide ions with benzyl chloride and bromide have been investigated in 90% ethanol solution. Semi-quantitative analysis of the results shows that the bond-formation is more important than the bond-breaking and furthermore in bond-formation the energy gain due to bond-formation is less than the increase in electron affinity of the nucleophile.

• Elastomers and Composites
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• v.53 no.2
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• pp.52-56
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• 2018

The present study examines the transformation of dynamic DSC data into the equivalent isothermal data for the formation kinetics of a polyurethane elastomer. The reaction of 2'-dichloro-4,4'-methylenedianiline (MOCA) with a PTMG/TDI-based isocyanate prepolymer was evaluated. DSC measurement was performed in the dynamic scanning mode with several different heating rates to obtain the reaction thermograms. Then, the data was transformed into the isothermal data through a procedure based on Ozawa analysis. The main feature of this procedure was the transformation of $({\alpha}-T)_{\beta}$ curves from dynamic DSC into $({\alpha}-t)_T$ curves using the isoconversional $(t-T)_{\alpha}$ diagram. Validity was discussed for the relationship between the dynamic DSC data and the transformed isothermal results.

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