• Bulletin of the Korean Chemical Society
• /
• v.23 no.2
• /
• pp.205-214
• /
• 2002

The reaction of gas-phase atomic hydrogen with hydrogen atoms chemisorbed on a silicon surface is studied by use of the classical trajectory approach. Especially, we have focused on the mechanism changes with the hydrogen surface coverage difference. On the sparsely covered surface, the gas atom interacts with the preadsorbed hydrogen atom and adjacent bare surface sites. In this case, it is shown that the chemisorption of H(g) is of major importance. Nearly all of the chemisorption events accompany the desorption of H(ad), i.e., adisplacement reaction. Although much less important than the displacement reaction, the formation of $H_2(g)$ is the second most significant reaction pathway. At gas temperature of 1800 K and surface temperature of 300 K, the probabilities of these two reactions are 0.750 and 0.065, respectively. The adsorption of H(g) without dissociating H(ad) is found to be negligible. In the reaction pathway forming $H_2$, most of the reaction energy is carried by $H_2(g)$. Although the majority of $H_2(g)$ molecules are produced in sub-picosecond, direct-mode collisions, there is a small amount of $H_2(g)$ produced in multiple impact collisions, which is characteristic of complex-mode collisions. On the fully covered surface, it has been shown that the formation of $H_2(g)$ is of major importance. All reactive events occur on a subpicosecond scale, following the Eley-Rideal mechanism. At gas temperature of 1800 K and surface temperature of 300 K, the probability of the $H_2(g)$ formation reaction is 0.082. In this case, neither the gas atom trapping nor the displacement reaction has been found.

• Transactions of the Korean Society of Automotive Engineers
• /
• v.20 no.6
• /
• pp.73-82
• /
• 2012

The main and side reactions of the three selective catalytic reduction (SCR) reactions with ammonia over a vanadium-based catalyst have been investigated using synthetic gas mixtures in the temperature range of $170{\sim}590^{\circ}C$. The three SCR reactions are standard SCR with pure NO, fast SCR with an equimolar mixture of NO and $NO_2$, and $NO_2$ SCR with pure $NO_2$. Vanadium based catalyst has no significant activity in NO oxidation to $NO_2$, while it has high activity for $NO_2$ decomposition at high temperatures. The selective catalytic oxidation of ammonia and the formation of nitrous oxide compete with the SCR reactions at the high temperatures. Water strongly inhibits the selective catalytic oxidation of ammonia and the formation of nitrous oxide, thus increasing the selectivity of the SCR reactions. However, the presence of water inhibits the SCR activity, most pronounced at low temperatures. In this study, the experimental results are analyzed by means of a dynamic one-dimensional isothermal heterogeneous plug-flow reactor (PFR) model according to the Eley-Rideal mechanism.

• Transactions of the Korean Society of Automotive Engineers
• /
• v.14 no.3
• /
• pp.125-132
• /
• 2006

Transient kinetics of $NH_3$ adsorption/desorption and of SCR(selective catalytic reduction) of NO with $NH_3$ were studied over vanadium based catalysts, such as $V_2O_5/TiO_2$ and $V_2O_5-WO_3/TiO_2$. In the present catalytic reaction process, NO adsorption is neglected while $NH_3$ is strongly chemisorbed on the catalytic surface. Accordingly, it is ruled out the possibility of a reaction between strongly adsorbed $NH_3$ and NO species in line with the hypothesis of an Eley-Rideal mechanism. The present kinetic model assumes; (1) non-activated $NH_3$ adsorption, (2) Temkin-type $NH_3$ coverage dependence of the desorption energy, (3) non-linear dependence of the SCR reaction rate on the $NH_3$ surface coverage. Thus, the surface heterogeneity for adsorption/desorption of $NH_3$ is taken into account in this model. The present study extends the pure chemical kinetic model based on a powdered-phase catalytic system to the chemico-physical one applicable to a realistic monolith reactor.