• Bulletin of the Korean Chemical Society
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• v.22 no.8
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• pp.889-896
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• 2001

The reaction of gas-phase atomic bromine with highly covered chemisorbed hydrogen atoms on a silicon surface is studied by use of the classical trajectory approach. It is found that the major reaction is the formation of HBr(g), and it proceeds th rough two modes, that is, direct Eley-Rideal and hot-atom mechanism. The HBr formation reaction takes place on a picosecond time scale with most of the reaction exothermicity depositing in the product vibration and translation. The adsorption of Br(g) on the surface is the second most efficient reaction pathway. The total reaction cross sections are $2.53{\AA}2$ for the HBr formation and $2.32{\AA}2$ for the adsorption of Br(g) at gas temperature 1500 K and surface temperature 300 K.

• Clean Technology
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• v.17 no.4
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• pp.370-378
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• 2011

Catalytic activity of $V_2O_5-WO_3/TiO_2$-based SCR catalyst was examined for the oxidation of gas-phase elemental mercury to oxidized mercury. Mercury species was not detected on the commercial SCR catalyst after the oxidation reaction of elemental mercury, regadless of the presence of HCl acting as oxidant and the reaction conditions. This suggests that elemental mercury oxidation by HCl could occur via a Eley-Rideal mechanism with gas phase or weakly-bound mercury on the surface of $V_2O_5-WO_3/TiO_2$ SCR catalyst. The activity for mercury oxidation was significantly increased with the increase of $V_2O_5$ loading, which indicates that $V_2O_5$ is the active site. However, turnover frequency for mercury oxidation was decreased with the increase of $V_2O_5$ loading, indicating the activity for mercury oxidation was strongly dependent on the surface structure of vanadia species. The activity for oxidation of elemental mercury under SCR condition was much less than that under oxidation condition at the same HCl concentration and reaction temperature.

• Applied Chemistry for Engineering
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• v.5 no.4
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• pp.580-587
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• 1994

The oxidative coupling of methane was studied kinetically using $Na^+(50wt%)/MgO$ catalyst at 710, 730, 750, 770 and $790^{\circ}C$ in a fixed bed flow reactor at the atmospheric pressure under differential conversion conditions. Through curve fitting, it was found that the Langmuir-Hinshelwood type mechanism was fitted to this reaction rather than Rideal-Redox type or Eley-Rideal type mechanism. Therefore, it was proposed that the $O_2{^-}$ or $O_2{^{2-}}$ species on the surface was related to the production of $CH_3{\cdot}$. The estimated activation energy of $CH_3{\cdot}$ production was about 39.3kcal/mol. Moreover, as the result of curve fitting, the stoichiometric coefficient of $O_2$ for the production of $CH_3{\cdot}$ to produce $CO_x$was approximately 1.5. Accordingly, it could be concluded that the $CH_3O_2{\cdot}*$ was prouduced through the partial oxidation of $CH_3{\cdot}$ with the surface oxygen.

• Bulletin of the Korean Chemical Society
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• v.24 no.7
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• pp.986-992
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• 2003

We have calculated the probability of the OH formation and energy deposit of the reaction exothermicity in the newly formed OH, particularly in its vibrational motion, in the gas-surface reaction O(g) + H(ad)/Si → OH(g) + Si on the basis of the collision-induced Eley-Rideal mechanism. The reaction probability of the OH formation increases linearly with initial excitation of the HSi vibration. The translational and vibrational motions share most of the energy when the H-Si vibration is initially in the ground state. But, when the initial excitation increases, the vibrational energy of OH rises accordingly, while the energies shared by other motions vary only slightly. The product vibrational excitation is significant and the population distribution is inverted. Flow of energy between the reaction zone and the solid has been incorporated in trajectory calculations. The amount of energy propagated into the solid is only a few percent of the available energy released in the OH formation.

• Solar Energy
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• v.15 no.2
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• pp.91-99
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• 1995

The influence of deposition parameters on the deposition of $SnO_2$ thin films by spray pyrolysis has been studied. In the case of spray solution with tile concentration of 0.01M, at low deposition temperature the deposition was controlled by surface reaction and portion controlled by mass transfer is increased with increasing deposition temperature to $400^{\circ}C$. Above $400^{\circ}C$, the deposition is controlled by mass transfer at low spray pressure, and by surface reaction at high spray pressure. As the concentration of spray solution increased the deposition rate increased, and in this experiment the deposition depends on the Rideal-Eley mechanism. The deposition rate increased with increasing substrate temperature up to $400^{\circ}C$ and then decreased due to homogeneous nucleation. The thickness of the deposit increased with increasing spray duration, and the adhesion between substrate and deposit was formed physically.

• Bulletin of the Korean Chemical Society
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• v.18 no.9
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• pp.985-994
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• 1997

The reaction of gas-phase atomic hydrogen with hydrogen atoms chemisorbed on Fe(110) surface is studied by use of classical trajectory procedures. Flow of energy between the reaction zone and bulk solid phase has been treated in the generalized Langevin equation approach. A London-Eyring-Polanyi-Sato energy surface is used for the reaction zone interaction. Most reactive events are found to occur in strong single-impact collisions on a subpicosecond scale via the Eley-Rideal mechanism. The extent of reaction is large and a major fraction of the available energy goes into the vibrational excitation of H2, exhibiting a vibrational population inversion. Dissipation of reaction energy to the heat bath can be adequately described using a seven-atom chain with the chain end bound to the rest of solid. The extent of reaction is not sensitive to the variation of surface temperature in the range of Ts=0-300 K in the fixed gas temperature, but it shows a minimum near 1000 K over the Tg=300-2500 K.

• Korean Journal of Materials Research
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• v.16 no.5
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• pp.323-328
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• 2006

In situ electrical conductivity measurements on $V_2O_5WO_3/TiO_2$ catalysts were carried out at between 100 and $300^{\circ}C$ under pure oxygen, NO and $NH_3$ to investigate the reaction mechanism for ammonia SCR (selective catalytic reduction) de NOX. The electrical conductivity of catalysts changed irregularly with supply of NO. It was, however, found that the electrical conductivity change with ammonia supply was regular and the increase of electrical conductivity was mainly caused by reduction of the labile surface oxygen. The electrical conductivity change of catalysts showed close relationship with the conversion rate of NOx. Variation of conversion rate in atmosphere without gaseous oxygen also showed that labile lattice oxygen is indispensable in the initial stage of the de NOx reaction. These results suggest that liable lattice oxygen acts decisive role in the de NOx mechanism. They also support that de NOx reaction occurs through the Eley?Rideal type mechanism. The amount of labile oxygen can be estimated from the measurement of electrical conductivity change for catalysts with ammonia supply. This suggests that measurement of the change can be used as a measure of the de NOx performance.

• Korean Chemical Engineering Research
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• v.50 no.2
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• pp.358-364
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• 2012

The kinetics of the Fischer-Tropsch synthesis and water gas shift reactions over a precipitated iron catalyst were studied in a 5 channel fixed-bed reactor. Experimental conditions were changed as follows: synthesis gas $H_2$/CO feed ratios of 0.5~2, reactants flow rate of 60~80 ml/min, and reaction temperature of $255{\sim}275^{\circ}C$ at a constant pressure of 1.5 MPa. The reaction rate of Fischer-Tropsch synthesis was calculated from Eley-Rideal mechanism in which the rate-determining step was the formation of the monomer species (methylene) by hydrogenation of associatively adsorbed CO. Whereas water gas shift reaction rate was determined by the formation of a formate intermediate species as the rate-determining step. As a result, the reaction rates of Fischer-Tropsch synthesis for the hydrocarbon formation and water gas shift for the $CO_2$ production were in good agreement with the experimental values, respectively. Therefore, the reaction rates ($r_{FT}$, $r_{WGS}$, $-r_{CO}$) derived from the reaction mechanisms showed good agreement both with experimental values and with some kinetic models from literature.

• Bulletin of the Korean Chemical Society
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• v.32 no.5
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• pp.1527-1533
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• 2011

The reaction of gas-phase atomic hydrogen with oxygen atoms chemisorbed on a silicon surface is studied by use of the classical trajectory approach. We have calculated the probability of the OH formation and energy deposit of the reaction exothermicity in the newly formed OH in the gas-surface reaction H(g) + O(ad)/Si${\rightarrow}$ OH(g) + Si. All reactive events occur in a single impact collision on a subpicosecond scale, following the Eley-Rideal mechanism. These events occur in a localized region around the adatom site on the surface. The reaction probability is dependent upon the gas temperature and shows the maximum near 1000 K, but it is essentially independent of the surface temperature. The reaction probability is also independent upon the initial excitation of the O-Si vibration. The reaction energy available for the product state is carried away by the desorbing OH in its translational and vibrational motions. When the initial excitation of the O-Si vibration increases, translational and vibrational energies of OH rise accordingly, while the energy shared by rotational motion varies only slightly. Flow of energy between the reaction zone and the solid has been incorporated in trajectory calculations, but the amount of energy propagated into the solid is only a few percent of the available energy released in the OH formation.

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1136-1144
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• 1999

The collision-induced reaction of gas-phase atomic hydrogen with hydrogen atoms chemisorbed on a silicon (001)-(2×1) surface is studied by use of the classical trajectory approach. The model is based on reaction zone atoms interacting with a finite number of primary system silicon atoms, which then are coupled to the heat bath, i.e., the bulk solid phase. The potential energy of the Hads‥Hgas interaction is the primary driver of the reaction, and in all reactive collisions, there is an efficient flow of energy from this interaction to the Hads-Si bond. All reactive events occur on a subpicosecond scale, following the Eley-Rideal mechanism. These events occur in a localized region around the adatom site on the surface. The reaction probability shows the maximum near 700K as the gas temperature increases, but it is nearly independent of the surface temperature up to 700 K. Over the surface temperature range of 0-700 K and gas temperature range of 300 to 2500 K, the reaction probability lies at about 0.1. The reaction energy available for the product states is small, and most of this energy is carried away by the desorbing H2 in its translational and vibrational motions. The Langevin equation is used to consider energy exchange between the reaction zone and the bulk solid phase.