• 한국분말재료학회지
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• 제10권6호
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• pp.422-429
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• 2003

The reduction mechanism of the composite powders mixed with $WO_3$ and CuO has been studied by using thermogravimetry (TG), X-ray diffraction, and microstructure analyses. The composite powders were made by simple Turbula mixing, spray drying, and ball-milling in a stainless steel jar with the ball to powder ratio of 32 to 1 at 80 rpm for 1 h without process controlling agents. It is observed that all the oxide composite powders are converted to W-coated Cu composite powder after reducing treatment under hydrogen atmosphere. For the formation mechanism of W-coated Cu composite powder, the sequential reduction steps are proposed as follows: CuO contained in the ball-milled composite powder is initially reduced to Cu at the temperature range from 20$0^{\circ}C$ to 30$0^{\circ}C$. Then, $WO_3$ powder is reduced to W $O_2$ via W $O_{2.9}$ and W $O_{2.72}$ at higher temperature region. Finally, the gaseous phase of $WO_3(OH)_2$ formed by reaction of $WO_2$ with water vapour migrates to previously reduced Cu and deposits on it as W reduced by hydrogen. The proposed mechanism has been proved through the model experiment which was performed by using Cu plate and $WO_3$ powder.

• 한국연소학회지
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• 제4권1호
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• pp.27-38
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• 1999

We constructed a wire-cylinder type pulsed corona discharge system for $NO_x$ removal, which was operated in room temperature. A emission spectrometer was built with a boxcar averager and monochrometer equipped with photo-multiplier tube detector. The sensitivity of the emission spectrometer was greatly improved by synchronizing the emission spectrometer with pulsed corona discharge system using a triggered spark-gap switch. $N_2$ spectrum($c^3{\Pi}_u{\rightarrow}X^1{\Sigma}_g{^+}$) was measured in the range of 300 - 450 nm and oxidizing OH radical emission($A^2{\Sigma}^+{\rightarrow}X^2{\Pi}$) was measured in case $N_2$ was supplied with water bubbling. As wet gas composition of inlet $N_2$ supplied in the discharge system increased, the intensity of OH emission was increased and saturated at wet gas composition 50%. We also investigated additive effect of $C_2H_4,\;H_2O,\;H_2O_2$ on the intensity of OR emission and $NO/NO_2/NO_x$ reduction and analysed the related reaction mechanism in corona discharge process. $H_2O_2$ additive increased the intensity of OH emission and $NO/NO_x$ reduction.

• 한국세라믹학회지
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• 제41권11호
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• pp.812-818
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• 2004

무수붕산(B$_2$O$_3$)과 활성탄소를 사용하여 질소 분위기에서 육방정 질화붕소(h-BN)을 합성할 때 그 생성조건 및 반응과정을 검토하였다. 육방정 질화붕소의 생성조건은 140$0^{\circ}C$ 이상에서 질화붕소가 합성되기 시작하여 155$0^{\circ}C$에서는 대부분의 합성이 이루어졌고, 그 이상의 온도에서는 생성이 크지 않았음이 확인되었다. 합성된 질화붕소의 입자 형상은 미세한 판상 결정을 나타내었다. 반응 과정은 무수붕산이 탄소에 의하여 환원되어 붕소로 기화됨과 동시에 공존하는 질소 가스와 반응하여 육방정 질화붕소로 합성되는 반응 경로를 따를 것으로 사료된다.

• Advances in environmental research
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• 제1권1호
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• pp.37-55
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• 2012

Here we show that perchlorate reduction during pitting corrosion of zero-valent titanium (ZVT) is likely caused by dissolved titanium species, especially Ti(II). Several possible mechanisms were suggested based on the literature and were evaluated based on experimental observations. Direct reduction of perchlorate on the bare metal of the ZVT electrode was thermodynamically infeasible due to the high anodic potential that was applied. Other potential mechanisms were considered such as reduction by small ZVT metal particles released from the electrode and direct reduction on the oxide layer of the electrode where potential was sufficiently reduced by a high ohmic potential drop. However, these mechanisms were not supported by experimental results. The most likely mechanism for perchlorate reduction was that during pitting corrosion, in which ZVT is partially oxidized to form dissolved ions such as Ti(II), which diffuse from the electrode surface and react with perchlorate in solution. This mechanism is supported by measurements of the dissolution valence and the molar ratio of ZVT consumed to perchlorate reduced (${\Delta}Ti(0)/{\Delta}ClO_4{^-}$). The results shown in this study demonstrate that ZVT undergoing pitting corrosion has the capability to chemically reduce perchlorate by producing dissolved Ti(II) and therefore, it has the potential to be applied in treatment systems. On the other hand, the results of this research imply that the application of ZVT undergoing pitting corrosion in treatment systems may not be feasible now due to several factors, including material and electricity costs and possible chloride oxidation.

• 한국자동차공학회논문집
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• 제15권3호
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• pp.166-173
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• 2007

A numerical study was conducted to have the effect of $CO_2$ addition to fuel on the chemical reaction mechanism with the change of the initial concentration of $CO_2$ and the axial velocity gradient. From this study, it was found that there were two serious effects of $CO_2$ addition on a non-premixed flame ; a diluent effect by the reactive species reduction and chemical effect of the breakdown of $CO_2$ by the third-body collision and thermal dissociation. Especially, the chemical effect was serious at the lower velocity gradient of the axial flow. It was certain that the mole fraction profile of $CO_2$ was deflected and CO was increased with the initial concentration of $CO_2$. It was also ascertained that the breakdown of $CO_2$ would cause the increasing of CO mole fraction at the reaction region. It was also found that the addition of $CO_2$ did not alter the basic skeleton of $H_2-O_2$ reaction mechanism, but contributed to the formation and destruction of hydrocarbon products such as HCO. The conversion of CO was also suppressed and $CO_2$ played a role of a dilution in the reaction zone at the higher axial velocity gradient.

• BMB Reports
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• 제32권4호
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• pp.358-362
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• 1999

dTDP-D-glucose 4,6-dehydratase as an oxidoreductase catalyzes the conversion of dTDP-D-glucose to dTDP-4-keto-6-deoxy-D-glucose, which is essential for the formation of 6-deoxysugars. dTDP-D-glucose 4,6-dehydratase shows remarkable sterochemical convergence in which displacement of the C-6 hydroxyl group by a C-4 hydrogen proceeds intramolecularly with inversion of configuration. The reaction mechanism is known to be oxidation, dehydration, and reduction by bases mediating proton transfer and $NAD^+$ cofactor. In this study, the bases in the active site domain are proposed to be His-79 and His-300 from a comparison of the peptides of the dehydratase and UDP-D-glucose epimerase. His-79 and His-300 were mutated to prepare the mutants H79L (mutation of histidine to leucine at the 79th amino acid) and H300A (mutation of histidine to alanine at the 300th amino acid) by site-directed mutagenesis. The H79L protein was inactive, showing that His-79 participates in the reaction mechanism.

• Bulletin of the Korean Chemical Society
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• 제31권10호
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• pp.2801-2805
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• 2010

A nucleophilic substitution reaction of 4-chloro-7-nitrobenzofurazan (NBF-Cl) with anilines in MeOH-MeCN mixtures was conducted at 25, 35, and $45^{\circ}C$. Based on the higher $\beta_{nuc}$ values (1.0 - 1.6) of the reaction and a good correlation of the rate constants with the reduction potentials of the aniline nucleophiles, the present reaction was initiated by a single electron transfer (SET). After this step, the reaction proceeds through a transition state similar to the normal $S_NAr$-Ad.E pathway.

• Bulletin of the Korean Chemical Society
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• 제17권3호
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• pp.269-273
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• 1996

Alkyl halides were reduced to the corresponding alkanes by the homonuclear bridging hydride, (μ-H)[(η5-MeCp)Mn(CO)2]2-PPN+ in THF at the elevated temperatures (40-60 ℃) under the pseudo first order reaction conditions where excess of alkyl halide was employed under nitrogen atmosphere. The reaction is of overall second order; first order with respect to [bridging hydride] and first order with respect to [alkyl halide] with the activation parameters, ΔH≠=28.93 kcal/mol and ΔS≠=17.95 e.u. The kinetic data, the ESR evidence and the reaction with cyclopropyl canbinyl bromide ensure that two possible reaction pathways are operable in this reaction: (1) concerted mechanism, and (2) single electron transfer pathway are in competition leading to the same product, the corresponding alkane.

• Bulletin of the Korean Chemical Society
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• 제11권4호
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• pp.303-306
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• 1990

Kinetic studies were carried out for the redox reaction of $[Co(NH_3)_4(C_2O_4)]^+$ with aqueous $[Fe(H_2O)_6]^{2+}$ solution in the present of $H^+$ by UV/VIS-spectrophotometric method. It was found that the order of $H^+$ for the reaction is first one in the higher $H^+$ concentration range of $1.67×10^{-1} M{\sim}1.00 M,$ while second order in the lower range of $6.30×10^{-2} M{\sim}1.67{\times}10^{-1} M.$ Reaction order of the substrates was found to be first order with respect to each of them. Accordingly overall reactions are third or fourth order. The results of calculation for the Extended Huckel Molecular Orbital theory contribute to estimate the preferred intermediates, bridging form of binuclear complex. On the basis of these results, we propose that this redox reaction proceed via inner-sphere reaction mechanism.

• 자원리싸이클링
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• 제26권5호
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• pp.54-60
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• 2017

본 연구에서는 $TiCl_4$ 투입시간의 효과가 $TiCl_4$ and Mg의 주어진 중량비율에서 Kroll반응에 미치는 효과를 조사하였다. 그리고 환원반응은 $TiCl_4$ 투입시간에 따라 온도변화를 측정하고, 반응 후 Ti 스폰지 단면과 외관을 관찰함으로써 조사되었다. Kroll 반응열 생성에 의한 온도 증분은 $TiCl_4$ 투입속도에 직선적으로 비례하는 것으로 파악되었다. $TiCl_4$ 투입시간과 환원조 온도 그래프를 보면, 초기 온도 피크가 주입조건에 무관하게 모두 관찰되었다. 이는 초기 Kroll 반응후 $MgCl_2$ 형성으로 인한 일시적인 반응 중단을 의미하는 것으로 해석된다. 또한 스폰지 단면을 관찰해보면, 구형 Mg 입자상이 $MgCl_2$ 내부에 다량으로 관찰되었다. 우리는 이것이 지속적인 Kroll 반응이 일어나도록 미반응 Mg 표면을 계속적으로 공급하는 과정이라 추론할 수 있다. 주사전자현미경으로 스폰지 외형을 관찰한 결과는 Kroll 반응된 Ti 입자들의 합체나 성장이 냉각속도에 의해 제어될 수 있음을 보여주었다.