• 한국세라믹학회지
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• 제35권12호
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• pp.1336-1336
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• 1998

2단계 열탄소환원법으로 탄화규소 휘스커를 Ar과 H2분위기에서 기상-고상, 2단계, 기상-액상-고상 성장기구를 통해 각각 합성하였다. Ar분위기에서 탄화규소 휘스커는 다음과 같은 반응기구로 성장하였다. SiO2(S)+C(s)-SiO(v)+CO(v) SiO(v)3CO(v)=SiC(s)whisker+2CO2(v) 2C(s)+2CO2(v)=4CO(v) 이때 전체 반응속도는 세번째 반응에 참여하는 탄소에 의해 지배되었다. 따라서 이 반응이 휘스커 합성의 율속반응으로 판단되었다. 한편 H2 분위기에서 탄화규소 휘스커는 다음과 같은 반응기구로 성장하였다.SiO2(s)+C(s)=SiO(v)+CO(v) 2C(s)+4H2(v)=2CH4(v) SiO(v)+2CH4(v)=SiC(s)whisker+CO(v)+4H2(v) 이때 전체 반응속도는 SiO(v) 기체의발생 속도에 의해 지배되었다. 따라서 첫번째 반응이 휘스커 합성의 율속 반응인 것으로 판단되었다.

• 한국세라믹학회지
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• 제35권12호
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• pp.1329-1336
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• 1998

A twt -step carbothermal reduction scheme has been employed for the synthesis of SiC whiskers in an Ar or a H2 atmosphere via vapor-solid two-stage and vapor-liquid-solid growth mechanism respectively. It has been shown that the whisker growth proceed through the following reaction mechanism in an Ar at-mosphere : SiO2(S)+C(s)-SiO(v)+CO(v) SiO(v)3CO(v)=SiC(s)whisker+2CO2(v) 2C(s)+2CO2(v)=4CO(v) the third reaction appears to be the rate-controlling reaction since the overall reaction rates are dominated by the carbon which is participated in this reaction. The whisker growth proceeded through the following reaction mechaism in a H2 atmosphere : SiO2(s)+C(s)=SiO(v)+CO(v) 2C(s)+4H2(v)=2CH4(v) SiO(v)+2CH4(v)=SiC(s)whisker+CO(v)+4H2(v) The first reaction appears to be the rate-controlling reaction since the overall reaction rates are enhanced byincreasing the SiO vapor generation rate.

• Bulletin of the Korean Chemical Society
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• 제16권4호
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• pp.310-315
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• 1995

The heterobimetallic anion, (OC)5CrMn(CO)5-M+ (M+=Na+, PPN+), which has a donor-acceptor metal-metal bond1, was reacted with allyl bromide to yield BrCr(CO)5- and Mn(CO)5(CH2CHCH2). The reaction mechanism has been proposed in terms of the consecutive reaction pathway in which Cr(CO)5(THF) is an important intermediate leading to the corresponding product. Counterion effect on this reaction was also evaluated and the results were compared with those of the corresponding reaction of the mononuclear carbonyl anion, Mn(CO)5-.

• Bulletin of the Korean Chemical Society
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• 제31권5호
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• pp.1295-1300
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• 2010

The $CO_2-CH_4$ reaction catalyzed by Ni/silicon wafers was kinetically studied by using a photoacoustic technique. The catalytic reaction was performed at various partial pressures of $CO_2$ and $CH_4$ (50 Torr total pressure of $CO_2/CH_4/N_2$) in the temperature range of 500 - $650^{\circ}C$ in a static reactor system. The photoacoustic signal that varied with the $CO_2$ concentration during the catalytic reaction was recorded as a function of time. Under the reaction conditions, the $CO_2$ photoacoustic measurements showed the as-prepared Ni thin film sample to be inactive for the reaction, while the $CO_2/CH_4$ reactions carried out in the presence of the sample pre-treated in $H_2$ at $600^{\circ}C$ were associated with significant time-dependent changes in the $CO_2$ photoacoustic signal. The rate of $CO_2$ disappearance was measured from the $CO_2$ photoacoustic signal data in the early reaction period of 50 - 150 sec to obtain precise kinetic data. The apparent activation energy for $CO_2$ consumption was determined to be 6.9 kcal/mol from the $CO_2$ disappearance rates. The partial reaction orders, determined from the $CO_2$ disappearance rates measured at various $PCO{_2}'S$ and $PCH{_4}'S$ at $600^{\circ}C$, were determined to be 0.33 for $CH_4$ and 0.63 for $CO_2$, respectively. Kinetic data obtained in these measurements were compared with previous works and were discussed to construct a catalytic reaction mechanism for the $CO_2-CH_4$ reaction over Ni/silicon wafer at low pressures.

• 한국결정성장학회지
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• 제5권2호
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• pp.109-121
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• 1995

SiC/Co 반응커플을 Ar/4 vol% $H_2$분위기하에서 $950^{\circ}C$에서 $1250^{\circ}C$ 범위에서 4시간에서 100시간까지 열처리하였다. $950^{\circ}C$ 이상의 온도에서의 고상반응으로 여러 가지 규소화물과 탄소석출이 형성되었다. 이 반응 zone에 있어서의 전형적인 반응층의 순서는 $SiC/CoSi + C/Co_2Si + C/Co_2Si/Co_2Si + C/{\cdots\cdots}/Co_2Si/Co$이었다. 그리고 탄소 석출거동을 동반한 주기적인 띠구조의 형성기구가 반응운동학과 열역학적인 고찰을 통하여 조사되어졌고 논하여졌다. 이 반응의 zone의 서장은 시간의 함수관계를 가지며 이러한 반응운동학이 반응상수의 측정을 통하여 제시되어진다. 또한 microhardness 측정을 통하여 반응 zone의 기계적인 물성이 조사되어졌다.

• 한국응용과학기술학회지
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• 제17권2호
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• pp.139-143
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• 2000

There appeared enhancements of the conversion of methane by adding a small amount of CO in the aromatization reaction of methane using the Mo-zeolite catalyst. In case of adding $CO_{2}$, $CO_{2}$ changed to CO first, and then the conversion reaction occurred. It was observed by using isotopes as reactants that CO is related to the aromatization reaction of methane.

• 자연과학논문집
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• 제4권
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• pp.85-93
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• 1991

$BaCO_3$와 $TiO_2$ 등 mole비 혼합물의 고상반응은 $BaCO_3 + TiO_2\longrightarrow$ $BaTiO_3 + CO_2$의 반응식에 따라 $CO_2$ gas가 발생된다. 이 분해과정을 DTA-TG를 사용하여 속도론적으로 고찰하였다. 그 결과는 다음과 같다. 1. $TiO_2$와 공존하는 $BaCO_3$는 순수한 $BaCO_3$보다 낮은 온도에서 분해된다. 그 이유는 생성물의 free energy가 감소되기 때문이다. 2. $BaCO_3$ 분해과정의 속도론적 고찰에 사용되는 식은 Jander's식보다는 Carter's식이 더욱 의미가 있으며 Carter's식에 의해 구해진 분해 활성화 에너지는 42.8Kcal/mol이다.

• Bulletin of the Korean Chemical Society
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• 제23권11호
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• pp.1513-1518
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• 2002

Kinetic studies on the water-gas shift reaction catalyzed by magnetite/chromium oxide and copper/zinc oxide were carried out by using an in situ photoacoustic spectroscopic technique. The reactions were performed in a closed-circulation reactor system using a differential photoacoustic cell at total pressure of 40 Torr in the temperature range of 100 to $350^{\circ}C.$ The CO2 photoacoustic signal varying with the concentration of CO2 during the catalytic reaction was recorded as a function of time. The time-resolved photoacoustic spectra obtained for the initial reaction stage provided precise data of CO2 formation rate. The apparent activation energies determined from the initial rates were 74.7 kJ/mol for the magnetite/chromium oxide catalyst and 50.9 kJ/mol for the copper/zinc oxide catalyst. To determine the reaction orders, partial pressures of CO(g) and H2O(g) in the reaction mixture were varied at a constant total pressure of 40 Torr with N2 buffer gas. For the magnetite/chromium oxide catalyst, the reaction orders with respect to CO and H2O were determined to be 0.93 and 0.18, respectively. For the copper/zinc oxide catalyst, the reaction orders with respect to CO and H2O were determined to be 0.79 and 0, respectively.

• Journal of Ceramic Processing Research
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• 제19권6호
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• pp.514-518
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• 2018

The direct carbon fuel cell (DCFC) has attracted researcher's attention recently, due to its high conversion efficiency and its abundant fuel, carbon. A DCFC mathematical model has developed in two-dimensional, lab-scale, and considers Boudouard reaction and carbon monoxide (CO) oxidation. The model simulates the CO production by Boudouard reaction and additional electron production by CO oxidation. The Boudouard equilibrium strongly depends on operating temperature and affects the amount of produced CO and consequentially affects the overall fuel cell performance. Two different operating temperatures (973 K, 1023 K) has been calculated to discover the CO production by Boudouard reaction and overall fuel cell performance. Moreover, anode thickness of the cell has been considered to find out the influence of the Boudouard reaction zone in fuel cell performance. It was found that in high temperature operating DCFC modeling, the Boudouard reaction cannot be neglected and has a vital role in the overall fuel cell performance.

• Bulletin of the Korean Chemical Society
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• 제19권4호
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• pp.462-466
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• 1998

The homobimetallic anion, $({\eta}^5-MeCp)Mn(CO)_2Mn(CO)_5-M^+\; (M^+=Na^+, PPN^+$) was disrupted by $PR_3\;(R=C_6H_5,\;C_2H_5,\;OCH_3)$ in THF at various temperatures (r.t. ∼65℃) under the pseudo first order reaction conditions where excess of $PR_3$ was employed under a nitrogen atmosphere. For the reaction involving $PPN^+$ analog, Mn-Mn heterolytic cleavage occurred, leading to $PPN^+Mn(CO)_5^-\; and \;({\eta}^5-MeCp)Mn(CO)_2PR_3$ as products; however, in case of $Na^+\; analog,\; Na^+$ seems to play a novel counter ion effect on the disruption reaction by transferring one terminal CO from the $Mn(CO)_5$ moiety on to the $({\eta}^5-MeCp)Mn(CO)_2$ of the corresponding homobimetallic complex, eventually resulting in $Na^+Mn(CO)_4PR_3^-\;and\;({\eta}^5-MeCp)Mn(CO)_3$. This reaction is of overall first order with respect to [homobimetallic complex] with the activation parameters (ΔH≠=23.0±0.7 kcal/mol, ΔS≠= - 8.7±0.8 e.u. for $Na^+$ analog; ΔH≠=28.8±0.4 kcal/mol, ΔS≠=15.7±0.6 e.u. for $PPN^+$ analog reaction).