• Bulletin of the Korean Chemical Society
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• 제35권11호
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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.

• 한국재료학회지
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• 제26권7호
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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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• 제12권3호
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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 ${\gamma}->{\delta}->{\alpha}-tocopherol$.

• 한국세라믹학회지
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• 제16권2호
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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.

• 한국산학기술학회논문지
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• 제8권5호
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• pp.1042-1046
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• 2007

본 연구에서는 제 3의 화학 원소 첨가에 의한 코발트 실리사이드와 니켈 실리사이드의 열적 안정성 향상 메카니즘을 조사하였다. 즉, Co-Si 시스템에 텅스텐을 첨가하는 경우 CoSi의 heat of formation이 증가하는 것으로 관찰되었다. 이러한 증가는 시스템 에너지 감속 속도의 최대화로 대변되는 실리사이드 형성 kinetics가 선호하는 glass의 형성을 억제하는 것으로 밝혀졌다. 이 경우 CoSi와 실리콘 기판 사이의 계면에 형성되는 다결정 구조는 glass의 self-diffusion보다 확산계수가 훨씬 작아 상 변이를 위해서는 보다 높은 열에너지를 요구하게 되어 궁극적으로 CoSi의 열적 안정성이 향상되는 것을 알 수 있었다.

• 시멘트
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• 통권31호
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• pp.29-35
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• 1969

• 대한화학회지
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• 제16권2호
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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.

• 대한화학회지
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• 제9권3호
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• pp.148-151
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• 1965

Benzyl chloride 및 bromide와 chloride 및 bromide ion 간의 반응을 90% ethanol 용액에서반응속도론적으로 연구하였다. 반 정량적인 결과의 해석은 bond-formation 이 bond-breaking보다 더 중요하고 또 결합형성 과정에서는 형성으로 얻은 energy보다는 nucleophile의 electron affinity의 증가로 인한 차이가 더 중요함을 보여주고 있다.

• Elastomers and Composites
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• 제53권2호
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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.

• 한국세라믹학회지
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• 제38권10호
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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.