Mixing-Limited Reactions in Porous Media

Transport in Porous Media - Acid mine drainage is generated when sulfide minerals are exposed to air and water through the porous subsurface, and it is significantly accelerated by the action of...     

Gas phase bimolecular chemistry of isomeric C3H6Br+ cations

The gas phase chemistry of C₃H₆Br⁺ cations generated via low energy electron impact on various dibromopropanes has been studied by using Fourier transform ion cyclotron resonance mass spectrometry. Neutral substrate molecules that have been selected to probe the bimolecular reactivity of the C₃H₆Br⁺ isomers are ammonia, methylamine, trimethylamine, cis-butene, and 2, 3-dimethyl-2-butene. At least three different isomers are characterized on the basis of their different reactivity toward the various substrate molecules. It is suggested that these isomers have (a) the 2-bromo-2-propyl cation structure, (b) the propylenebromomum ion structure, and (c) the cyclic four-membered trimethylenebromonium ion structure. The 2-bromo-2-propyl cations react predominantely via proton transfer. This reaction is hampered for the propylenebromonium ions, which react mainly as electrophiles or bromanyl cation donors. Cyclic trimethylenebromoruum ions react predominantly via adduct formation, even under low pressure conditions, which implies that tturd body collisions are not the only stabilization mechanism.     

Effect of the dielectric-constant mismatch and magnetic field on the binding energy of hydrogenic impurities in a spherical quantum dot

Within the effective mass approximation and variational method the effect of dielectric constant mismatch between the size-quantized semiconductor sphere, coating and surrounding environment on impurity binding energy in both the absence and presence of a magnetic field is considered. The dependences of the binding energy of a hydrogenic on-center impurity on the sphere and coating radii, alloy concentration, dielectric-constant mismatch, and magnetic field intensity are found for the GaAs–Ga_1−xAl_xAs–AlAs (or vacuum) system.     

Acetaldehyde adsorption and catalytic decomposition on Pd(1 1 0) and the dissolution of carbon

The reaction of acetaldehyde with the Pd(1 1 0) surface has been studied using a molecular beam reactor, TPD and LEED. Below 270 K acetaldehyde sticks to the surface with a high initial probability (∼0.8), but no gas phase products evolve. When the reaction is run at >270 K, hydrogen evolves into the gas phase early in the reaction together with methane in a non-steady-state fashion, but above 300 K there is a very efficient steady-state catalytic reaction at the surface; this reaction is the decarbonylation of acetaldehyde to produce methane and carbon monoxide in the gas phase. This behaviour continues up to about 400 K. However, when acetaldehyde is dosed at 423 K, the reaction rate slowly evolves through a maximum to a very low catalytic rate. Upon carrying out reactor experiments at 473 K and above, the reaction mechanism changes to total dehydrogenation, and CO and H₂ are produced at high steady-state rate, not withstanding the fact that carbon is continually being deposited onto the surface. This carbon does not appear to affect the reaction, which takes place on a surface with a c(2 × 2)-C layer present, since the extra carbon is lost from the reaction zone by diffusion into the bulk of the crystal.     

On the correlation of a group of rankings with an external ordering relative to the internal concordance

A method is presented for comparing the strength of agreement of a group rankings with an external ordering to the corresponding measure of concordance within the group. While the procedure is not model dependent, we illustrate the characteristics of interest using an existing model for a nonnull distribution for a population of rankings. U-statistics and a jackknife with adjusted degrees of freedom are employed to set approximate confidence intervals on the contrast between the two measures of rank order agreement.     

Distributed feedback fiber laser pumped by multimode laser diodes

A distributed feedback fiber laser made of highly Er-Yb codoped phosphate glass fiber has been demonstrated experimentally. Efficient pump absorption allows for multimode pumping into the cladding of the active fiber. Output powers up to 160 mW have been achieved. The 35 mm long fiber laser device emits with >50 dB side mode suppression ratio.