• 한국자동차공학회논문집
• /
• 제21권2호
• /
• pp.37-44
• /
• 2013

Generally, a reduced chemical mechanism of n-heptane is used as chemical fuel of a 3-D diesel engine simulation because diesel fuel consists of hundreds of chemical components and various chemical classes so that it is very complex and large to use for the calculation. However, the importance of fuel in a 3-D simulation increases because detailed fuel characteristics are the key factor in the recent engine research such as homogeneous charged compression ignition engine. In this study, normal paraffin, iso paraffin and aromatics were selected to represent diesel characteristics and n-dodecane was used as a representative normal paraffin to describe the heavy molecular weight of diesel oil (C10~C20). Reduced kinetics of iso-octane and toluene which are representative species of iso paraffin and aromatics respectively were developed in the previous study. Some species were selected based on the sensitivity analysis and a mechanism was developed based on the general oxidation scheme. The ignition delay times, maximum pressure and temperature of the new reduced n-dodecane chemical mechanisms were well matched to the detailed mechanism data.

• Bulletin of the Korean Chemical Society
• /
• 제28권10호
• /
• pp.1797-1802
• /
• 2007

The kinetics and mechanism of the nucleophilic substitution reactions of diphenyl phosphinic (1) and thiophosphinic (2) chlorides with substituted X-pyridines are investigated kinetically in acetonitrile at 35.0 and 55.0 oC, respectively. A concerted mechanism with backside nucleophilic attack is proposed for the pyridinolysis of 1, on the basis of the linear Bronsted plot with the βX value of 0.68. In the case of the pyridinolysis of 2, the Hammett and Bronsted plots are biphasic concave upwards with the break point at 3- phenyl pyridine. These results indicate a change in mechanism from a concerted SN2(P) process with direct backside nucleophilic attack for less basic nucleophiles (X = 3-CN-3-Ph) to a stepwise process with frontside attack for more basic nucleophiles (X = 4-MeO-3-Ph). Apparent secondary inverse kinetic isotope effects with deuterated pyridine (C5D5N), kH/kD < 1, are observed for the pyridinolysis of 1 and 2.

• Macromolecular Research
• /
• 제14권5호
• /
• pp.491-498
• /
• 2006

The thermal degradation of poly(hexamethylene guanidine) phosphate (PHMG) was studied by dynamic thermogravimetric analysis (TGA) and pyrolysis-GC/MS (p-GC). Thermal degradation of PHMG occurs in three different processes, such as dephosphorylation, sublimation/vaporization of amine compounds and decomposition/ recombination of hydrocarbon residues. The kinetic parameters of each stage were calculated from the Kissinger, Friedman and Flynn-Wall-Ozawa methods. The Chang method was also used for comparison study. To investigate the degradation mechanisms of the three different stages, the Coats-Redfern and the Phadnis-Deshpande methods were employed. The probable degradation mechanism for the first stage was a nucleation and growth mechanism, $A_n$ type. However, a power law and a diffusion mechanism, $D_n$ type, were operated for the second degradation stage, whereas a nucleation and growth mechanism, $A_n$ type, were operated again for the third degradation stage of PHMG. The theoretical weight loss against temperature curves, calculated by the estimated kinetic parameters, well fit the experimental data, thereby confirming the validity of the analysis method used in this work. The life-time predicted from the kinetic equation is a valuable guide for the thermal processing of PHMG.

• 한국수소및신에너지학회논문집
• /
• 제22권4호
• /
• pp.458-464
• /
• 2011

Recently, one of the hydrogen production methods has attracted using dense metallic membrane. It has high hydrogen permeation and selectivity which hardly could adopt industrial product because of high cost, hydrogen embrittlment and thermal stability. Meanwhile, vanadium has high hydrogen solubility and it use to instead of Pd-Ag amorphous membrane. Aluminum carried out blocking hydrogen diffusion on grain boundary therefore protecting hydrogen embrittlement. Most of dense metallic membrane is solution diffusion mechanism. The solution diffusion mechanism was very similar hydrogen storing steps such as steps of metal hydride. Thus, V-Al composites were fabricated to use hydrogen induced mechanical alloying. The fabricated V-Al composites were characterized by XRD, SEM, EDS and simultaneous TG/DSC analyses. The hydrogenation behaviors were evaluated using a Sievert's type automatic PCT apparatus. The hydrogenation behaviors of V-Al composites was evaluated too low hydrogen stored capacity and fast hydrogenation kinetics. In PCI results, V-Al composites had low hydrogen solubility, in spite of that, hydrogen kinetics was calculated very fast and hydrogen absorption/desorption contents were same capacity.

• 한국세라믹학회지
• /
• 제35권11호
• /
• pp.1162-1170
• /
• 1998

PbO-TiO2-B2O3-BaO 계 유리상에서 PbTiO3의 결정화 메커니즘에 대한 이론적 고찰 및 전자현미경 관찰 그리고 결정화 기구의 열시차 분석에 대한 응용성을 조사하였다. 열시차 분석에 대한 Kissinger 식의 응용은 DTA 분석시 시료내 핵밀도가 변하지 않을 때 적용할 수 있으며, 표면결정화를 유도하기 위해 분말시료를 사용하는 경우도 활성화 에너지를 시료의 결정화 메커니즘에 크게 영향을 받는다. Ozawa 식에 의한 Avrami parameter n은 전자현미경 관찰에 의해 파악된 결정화메커니즘과 잘 일치하고 있었으며, 수정 Kissinger 식은 시료의 결정화 메커니즘을 반영하고 있어 시료의 전처리와 관계없이 참값의 활성화에너지를 구할 수 있다.

• 환경위생공학
• /
• 제14권2호
• /
• pp.113-119
• /
• 1999

In this study, the incineration of MEK and toluene was studied on a Pt supported alumina catalyst at temperature range from 200 to $350^{\circ}C$. An approach based on the Mars-van Krevelen rate model was used to explain the results. The object of this study was to study the kinetic behavior of the platinum catalyst for deep oxidation. The conversions of MEK and toluene were increased as the inlet concentration was decreased and the reaction temperature was increased. The maximum deep conversion of MEK and toluene were 91.81% and 55.69% at $350^{\circ}C$, respectively. The ${\kappa}_3$ constant increases with temperature faster than the ${\kappa}_1$ constant, that is, the surface concentration of ($VOCs{\cdots}O$) is higher than that of (O) at higher temperature according to the Mars-van Krevelen mechanism. Also the activation energy of toluene was larger than MEK for toluene is aromatic compound which have stronger bonding energy.Therefore, the catalytic incineration kinetics of MEK and toluene with Mars-van Krevelen mechanism could be used as the basic data for industrial processes.

• ETRI Journal
• /
• 제19권1호
• /
• pp.26-35
• /
• 1997

The substrate effects on solid-phase crystallization of amorphous silicon (a-Si) films deposited by low-pressure chemical vapor deposition (LPCVD) using $Si_2H_6$ gas have been extensively investigated. The a-Si films were prepared on various substrates, such as thermally oxidized Si wafer ($SiO_2$/Si), quartz and LPCVD-oxide, and annealed at 600$^{\circ}C$ in an $N_2$ ambient for crystallization. The crystallization behavior was found to be strongly dependent on the substrate even though all the silicon films were deposited in amorphous phase. It was first observed that crystallization in a-Si films deposited on the $SiO_2$/Si starts from the interface between the a-Si and the substrate, so called interface-interface-induced crystallization, while random nucleation process dominates on the other substrates. The different kinetics and mechanism of solid-phase crystallization is attributed to the structural disorderness of a-Si films, which is strongly affected by the surface roughness of the substrates.

• Bulletin of the Korean Chemical Society
• /
• 제20권12호
• /
• pp.1487-1492
• /
• 1999

The kinetics of oxidation of substituted styryl 4-biphenyl ketones and of substituted styryl 2-fluorenyl ketones by pyridinium chlorochromate (PCC) have been studied in 90% acetic acid- 10% water (v/v) containing perchloric acid and NaClO₄ at $10^0,\;20^0,\;30^0$ and 40℃. The reactions are first order in styryl ketones and PCC. The second order rate constants are well correlated only with σ$^+$ constants implying development of positive charge adjacent to benzene ring in the transition state. The effects of varying [HClO₄] and the percentage of acetic acid on the reactions have also been analysed. A mechanism involving nucleophilic attack of PCC leading to an unsymmetric intermediate from which epoxides are formed is proposed.

• 한국응용과학기술학회지
• /
• 제9권2호
• /
• pp.119-126
• /
• 1992

The kinetics of the hydrolysis of indolylacrylophenone derivatives(IA) was investigated by ultraviolet spectrophotometry in 30% dioxane-$H_2O$ at 25$^{\circ}C$ Rate equations were obtained over a wide pH range. On the basis of rate equation, general base catalysis and Hammett's plot, the mechanism of hydrolysis to the (IA) were proposed: Below pH 3.0, the hydrolysis of (IA) was proportional to hydronium ion concentration, between pH 4.0${\sim}$9.0 neutral water molecule and hydroxide ion were added to carbon-carbon double bond and over pH 10.0 hydrolysis of (IA) was proportional to hydroxide ion concentration.

• 한국가스학회:학술대회논문집
• /
• 한국가스학회 2005년도 추계학술발표회 논문집
• /
• pp.83-87
• /
• 2005

The kinetics of the direct synthesis of DME was studied under different conditions over a temperature range of $220\~280^{\circ}C$, syngas ratio $1.2\~ 3.0$ All experiment were carried out over hybrid catalyst, composed to a methanol synthesis catalyst (Cu/ZnO/$Al_2O_3$) and a dehydration Catalyst ($\gamma$-Al_2O_3$) The observed reaction rate qualitatively follows a Langmiur-Hinshellwood type of reaction mechanism. Such a mechanism is considered with three reaction, methanol synthesis, methanol dehydration and water gas shift reaction. From a surface reaction with dissociative adsorption of hydrogen, methanol and water, individual reaction rate was determined