The collimation angle shift of desorbing product N2 in a steady-state N2O+CO reaction on Rh(110).

The angular distribution of desorbing product N2 was studied in N2O decompositions on Rh(110) in the temperature range of 60-700 K. The N2 desorption collimates along 62 degrees -68 degrees off normal toward either the [001] or [001] direction in a transient N2O decomposition below ca. 470 K or in the steady-state N2O+CO reaction above 540 K. In the steady-state reaction at the temperature from ca. 470 to 540 K, however, the collimation angle shifts from 62 degrees to 45 degrees with decreasing surface temperature. This angle shift is ascribed to the steric hindrance by coadsorbed CO because the N2 collimation in transient N2O decomposition at around 65 degrees is recovered in the range of 380-500 K by an abrupt CO pressure drop followed by the decrease in CO coverage. N2O is oriented along the [001] direction before dissociation. A scattering model of the nascent N2 by adsorbed CO is proposed, yielding smaller collimation angles.

Dechlorination/hydrogenation and destruction reactions of PCDDs in OCDD-added fly ash heated under vacuum.

Octachlorodibenzo-p-dioxin (OCDD)-added, pretreated fly ash was heated under vacuum at sample temperatures ranging from T(s)=450 to 650 K. The fly ash and liquid nitrogen-cooled trap samples were analyzed for DD/DF through OCDD/DF. The total amounts of DD through OCDD decrease with increasing T(s), which indicates that dechlorination/hydrogenation (DCH) reactions are not the only reaction channels. Reduction of toxic equivalent (TEQ) for PCDDs by more than 99% was achieved in the fly ash by the vacuum heat treatment at T(s)=650 K for 4 h. The total amount of PCDDs and DD detected in the liquid nitrogen-cooled trap relative to that of added OCDD was about 17%, i.e., PCDDs and DD which were adsorbed to the fly ash surfaces can evaporate into the gaseous phase. The difference between the evaporation behavior of PCDDs in the present and the previous studies is discussed in the light of their states of existence.

Spatial distributions of desorbing products in steady-state NO and N2O reductions on Pd(110).

The angular and velocity distributions of desorbing product N(2) were examined over the crystal azimuth in steady-state NO+CO and N(2)O+CO reactions on Pd(110) by cross-correlation time-of-flight techniques. At surface temperatures below 600 K, N(2) desorption in both reactions splits into two directional lobes collimated along 41 degrees -45 degrees from the surface normal toward the [001] and [001] directions. Above 600 K, the normally directed N(2) desorption is enhanced in the NO reduction. Each product desorption component, as well as CO(2), shows a fairly asymmetric distribution about its collimation axis. Two factors, i.e., the anisotropic site structures and the reactant orientation and movements, are operative to induce such asymmetry, depending on the product emission mechanism.

Removal of PCDDs/DFs and dl-PCBs in MWI fly ash by heating under vacuum.

Temperature dependence of PCDD/DF and dioxin-like polychlorinated biphenyl (dl-PCB) concentrations in fly ash from a municipal waste incinerator (MWI) heated under vacuum has been investigated as a function of sample temperature ranging from T(s)=425 to 800 K to find out if PCDDs/DFs in fly ash evaporate and are trapped in a liquid nitrogen-cooled trap. The results show that more than 99.98% of PCDDs/DFs in TEQ is removed from fly ash by vacuum heat treatment at T(s)>650 K for 4 h. Almost no PCDDs/DFs were detected in the liquid nitrogen-cooled trap. Homologue distributions indicate that dechlorination/hydrogenation (DCH) reactions proceed in fly ash at T(s)>450 K. Arrhenius rate parameters for the DCH reactions have been determined for each homologue assuming that only DCH reactions occur. The fly ash heated under vacuum at 650 or 800 K was reheated at 573 K (300 degrees C) in a stream of dry or humid air to see how much PCDDs/DFs and dl-PCBs are regenerated. We have found that (1) PCDDs/DFs are regenerated in both 650 K and 800 K treated fly ash, whereas dl-PCBs are regenerated in 650 K treated fly ash, (2) formation of PCDFs predominates over that of PCDDs or dl-PCBs, and (3) less chlorinated homologues are abundant for PCDDs/DFs and dl-PCBs.